Determination of Biogenic Amine Level Variations upon Storage, in Chicken Breast Coated with Edible Protective Film.

A new chitosan-based protective film containing rosemarinic acid (0.282% w/w) has been elaborated. The film was formed from a water-oil emulsion system and applied to poultry meat samples using a dip-coating technique. Various physicochemical parameters of the coatings, such as thickness, Young's modulus, elongation at break, water vapor transmission rates, and antioxidant activity, were tested with free-standing film samples peeled from a Petri dish. Compared to neat chitosan films obtained similarly, new films cast from the emulsion showed significantly better elasticity (Young's modulus was diminished from 1458 MPa to about 29 MPa). Additionally, barrier properties for moisture transition decreased from 7.3 to 5.8 g mm m-2 day-1 kPa-1. The coated poultry samples were subsequently evaluated in juxtaposition with uncoated ones in a storage test. Levels of selected biogenic amines (histamine, tyramine, tryptamine, phenylethylamine, putrescine, cadaverine, spermine, and spermidine), total bacterial count, and lipid oxidation levels in the meat samples were analyzed during storage at 4 °C (up to 96 h). The results obtained for the biogenic amines, total bacterial content, calculated biogenic amine index, and the ratio of spermidine to spermine in meat samples suggest the advantage of the proposed coatings with rosmarinic acid in protecting poultry meat against environmental factors and rapid spoilage.

New Water-Soluble (Iminomethyl)benzenesulfonates Derived from Biogenic Amines for Potential Biological Applications.

In this paper, a highly efficient and straightforward method for synthesizing novel Schiff bases was developed by reacting selected biogenic amines with sodium 2-formylbenzene sulfonate and sodium 3-formylbenzene sulfonate. 1H and 13C NMR, IR spectroscopy, and high-resolution mass spectrometry were used to characterize the new compounds. The main advantages of the proposed procedure include simple reagents and reactions carried out in water or methanol and at room temperature, which reduces time and energy. Moreover, it was shown that the obtained water-soluble Schiff bases are stable in aqueous solution for at least seven days. Additionally, the antioxidant and antimicrobial activity of synthesized Schiff bases were tested.

The Selection of the Best Derivatization Reagents for the Determination of Polyamines in Home-Made Wine Samples.

The procedures of putrescine, spermine, spermidine, and cadaverine derivatization using 2-chloro-1,3-dinitro-5-(trifluoromethyl)benzene, 1-fluoro-2-nitro-4-(trifluoromethyl) benzene, and 3,5-bis-(trifluoromethyl)phenyl isothiocyanate for chromatographic determination in home-made wine samples are compared in the present study. The procedures discussed were compared regarding simplicity, linearity, precision, and accuracy. The polyamines derivatives were isolated and characterized by X-ray crystallography and 1H, 13C, and 19F NMR spectroscopy. The obtained structures of aliphatic amines showed that all amino groups, four in spermine, two in putrescine and cadaverine, and three in spermidine, regardless of the applied reagent, were substituted. The applicability of the described procedures was tested during the chromatographic analysis of the compounds' content in home-made wines. For this purpose, a simple and environmentally friendly sample preparation procedure was developed. The obtained results present the derivatization of polyamines with 1-fluoro-2-nitro-4-(trifluoromethyl)benzene as a better choice for the determination of these compounds in food samples.

Simple and Effective Derivatization of Amino Acids with 1-Fluoro-2-nitro-4-(trifluoromethyl)benzene in a Microwave Reactor for Determination of Free Amino Acids in Kombucha Beverages.

Kombucha is a fermentation product of sweetened tea with a symbiotic culture of acetic acid and yeast bacteria, consumed worldwide for its health-promoting properties. Few reports can be found about free amino acids among the health-promoting compounds found and determined in kombucha. These compounds influence the sensory properties of kombucha, and they are precursors of bioactive compounds, which have a significant role as neurotransmitters and are involved in biological functions. The presented studies proposed a convenient, simple, and "more green" procedure of the synthesis of amino acid derivatives, assisted by microwave energy, followed by chromatographic determination. The structure of 1-Fluoro-2-nitro-4-(trifluoromethyl)benzene was used as a suitable reagent for the derivatization of free amino acids in fermented kombucha beverages prepared from selected dry fruit such as Crataegus L., Morus alba L., Sorbus aucuparia L., Berberis vulgaris L., Rosa canina L., and black tea. The obtained results were discussed regarding the tested beverages' application as a source of amino acids in one's daily diet. The obtained results point out that the proposed microwave-assisted derivatization procedure prior to HPLC analyses allows for a significant time reduction and the limitation of using organic reagents.

Phenolipids as new food additives: from synthesis to cell-based biological activities.

Increasing interest has been shown in phenolic compounds for enhancing food quality, but their hydrophilicity restricts application in lipophilic systems. Therefore, in this study, twelve hydroxycinnamates derivatives (alkyl and steryl esters of sinapic acid (SA), caffeic acid (CA), and ferulic acid [FA]) were synthesised and evaluated for antioxidant and cytotoxic characteristics. CA esters had the highest radical scavenging activity (RSA) analysed by 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) assays. Values of inhibitory concentration (IC50) of synthesised compounds were related to their structure and lipophilicity. The effect of these hydroxycinnamic acid esters on the antioxidant potential of real samples (rapeseed oil, margarine and mayonnaise) was estimated. None of the investigated derivatives significantly affected the viability of the model intestinal cells Caco2, while the octyl esters demonstrated a toxic effect at low concentrations. The synthesised esters exerted cytotoxic and anti-proliferative effects against transformed cell lines (HeLa and A549). Octyl esters were potent anticancer compounds on two human cancer cell lines. The synthesised phenolipids, as valuable and safe antioxidant additives, can find broader applications in the production of fat-based products to prevent oxidation processes, extend their shelf life and improve quality.

Steryl Sinapate as a New Antioxidant to Improve Rapeseed Oil Quality during Accelerated Shelf Life.

In recent years, steryl esters have become an attractive for the cosmetic, pharmaceutical, and food industries. Hence, the effect of exogenous antioxidant, ß-sitosteryl sinapate on oxidative stability and antioxidant activity (AA) of refined rapeseed oil was evaluated by the accelerated shelf-life test. Oxidative parameters of refined rapeseed oil-peroxide value (PV), anisidine value (p-AnV), acid value (AV), and spectrophotometric indices (K232, K268)-increased during storage. However, the addition of ß-sitosteryl sinapate caused a decrease of the primary and secondary oxidation products in the supplemented oils in comparison with the control sample. Moreover, oils with steryl ester had higher AA than oil without the synthetic antioxidant. The accelerated storage negatively affected the antioxidant potential of refined and enriched oils causing the AA decrease by 25-54% and 7-15%, respectively. Studies have consistently demonstrated beneficial associations between the presence of ß-sitosteryl sinapate in oil samples and the inhibition of their oxidative degradation under the accelerated conditions. Additionally, the possibility of using the synchronous fluorescence (SF) spectroscopy and excitation-emission matrix (EEM) fluorescence spectroscopy for identification and observing changes in main fluorescent components present in non-supplemented and supplemented rapeseed oils during the accelerated storage was attempted.

Synthesis of Steryl Hydroxycinnamates to Enhance Antioxidant Activity of Rapeseed Oil and Emulsions.

In recent years, steryl esters have found potential applications in food, pharmaceutical and cosmetic industries. Therefore, three hydroxycinnamate steryl esters (HSEs): ß-sitosteryl sinapate (ß-SSA), ß-sitosteryl caffeate (ß-SCA), and ß-sitosteryl ferulate (ß-SFA) were synthesized by chemical approach and their antioxidant activity (AA) were analyzed by 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulphonic acid (ABTS) assays. The values of inhibitory concentration (IC50) of each ester needed to inhibit 50% of the DPPH radical (IC50(DPPH) = 238.9, 78.3, 290.0 µmol/L for ß-SSA, ß-SCA, and ß-SFA, respectively) and ABTS radical cation (IC50(ABTS) = 174.6, 106.7, 206.0 µmol/L for ß-SSA, ß-SCA, and ß-SFA, respectively) were estimated and compared with antioxidant potential of phenolic acids. Moreover, the effect of HSEs addition in the concentrations range between 0.01% and 0.5% on the AA of refined rapeseed oil, mayonnaise and margarine was evaluated. Chemical structures of the synthesized HSEs and their concentrations strongly affect the AA of fat products. Oil and emulsions supplemented with higher concentrations of HSEs had significantly higher AA than control samples. Unfortunately, lower concentrations of HSEs (0.01% and 0.02%) did not increase the AA of fat products. However, steryl phenolates added in higher amounts can be considered as potential antioxidants delaying the oxidation processes of studied fats.

Chiral terpene auxiliaries V: Synthesis of new chiral γ-hydroxyphosphine oxides derived from α-pinene.

New chiral regioisomeric γ-hydroxyphosphine ligands were synthesized from α-pinene. The key transformation was the thermal [2,3]-sigmatropic rearrangement of allyldiphenylphosphinites, obtained from (1R,2R,4S,5R)-3-methyleneneoisoverbanol and (1R,2R,3R,5R)-4-methyleneneoisopinocampheol, to allylphosphine oxides. Hydroxy groups were introduced stereoselectively through a hydroboration-oxidation reaction proceeding from the less hindered site providing a trans relationship between the hydroxy and the phosphine substituents.

Bioselectivity Induced by Chirality of New Terpenyl Organoselenium Compounds.

A series of new chiral benzisoselenazol-3(2H)-ones substituted on the nitrogen atom with three monoterpene moieties-p-menthane, pinane and carane-was synthesized. The compounds were obtained by the reaction of 2-(chloroseleno)benzoyl chloride with an appropriate terpene amine, first synthesized by a multistep methodology starting from the corresponding alcohol (p-menthane system) or alkene (pinene and carene systems). Compounds were tested as antioxidants and anticancer agents. The N-isopinocampheyl-1,2-benzisoselenazol-3(2H)-one was the best peroxide scavenger and antiproliferative agent on the human promyelocytic leukemia cell line HL-60. The N-menthyl-1,2-benzisoselenazol-3(2H)-one revealed the highest anticancer potential towards breast cancer line MCF-7. The influence of structure and chirality on the bio-activity of the obtained organoselenium compounds was thoroughly evaluated.

The Intraneural Ganglion Cyst of the Tibial Nerve: A Case Report and Review of Literature.

INTRODUCTION: The intraneural ganglion cyst of the tibial nerve is very rare, especially at the level of an ankle and a foot. There are 15 previous reports of the tibial intraneural ganglion cyst within the tarsal tunnel or the popliteal fossa. The authors present an infrequent case of the tibial intraneural ganglion at the level of the tarsal tunnel diagnosed by an ultrasound examination and provide a review of the case studies described earlier in the available literature. CASE REPORT: Patient, a 37-year-old Caucasian male, was admitted to the orthopedic outpatient clinic with the pain and the paresthesia of medial half of his right foot. He underwent an ultrasound examination which diagnosed the intraneural ganglion cyst of the tibial nerve. The patient was qualified for surgical treatment. The nerve was compressed to only 30% of its diameter. The nerve function returned in4 months post-operative and the patient presented no signs of the nerve disorder. CONCLUSION: In almost all analyzed articles, authors suggest that pathogenesis is connected with the retrograde extension of the synovial fluid from the adjacent joints or with the trauma. In our study, there was no history of trauma and there was no connection with the joint during operation. We believed that the pathogenesis of this disorder was multifactorial.

Synthesis of novel octyl sinapate to enhance antioxidant capacity of rapeseed-linseed oil mixture.

BACKGROUND: Lipophilisation allows the formation of new functionalised antioxidants having beneficial properties compared to natural hydrophilic phenolic acids. Therefore, this work focused on the synthesis of lipophilic antioxidants, such as a new octyl sinapate, octyl caffeate and octyl ferulate using the modified Fischer esterification of selected hydroxycinnamic acids with 1-octanol. RESULTS: The lipophilic octyl sinapate was obtained for the first time with satisfactory yield (83%) after purification by column chromatography. The identity of the synthesised phenolipids was confirmed by chromatographic and spectroscopic analyses. Antioxidant capacity of phenolipids was determined by DPPH (IC50 = 35.87-52.24 µg mL-1 ) and ABTS (IC50 = 39.45-48.72 µg mL-1 ) methods and compared with IC50 values (7.37-35.30 µg mL-1 and 7.55-41.67 µg mL-1 , respectively) for well known antioxidants. The antioxidant capacity of rapeseed-linseed oil enriched with the purified esters was about two to 30 times higher in comparison with a non-supplemented oil. CONCLUSION: The novel octyl sinapate as well as octyl caffeate and octyl ferulate have antioxidant properties and lipophilic character, therefore they may be added to vegetable oils as potential antioxidants for tackling oxidative processes. © 2017 Society of Chemical Industry.

Application of 3,5-bis-(trifluoromethyl)phenyl isothiocyanate for the determination of selected biogenic amines by LC-tandem mass spectrometry and 19F NMR.

3,5-Bis-(trifluoromethyl)phenyl isothiocyanate, was used as a convenient reagent for the derivatization of histamine, tyramine, tryptamine and 2-phenylethylamine, which eliminates the purification step. The obtained derivatives were determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Additionally, the total amount of these amines was determined by 19F nuclear magnetic resonance analysis. The procedures were optimized and validated for linearity, limit of detection and quantification, intra- and inter-day precision and recovery resulting in good reproducibility and accuracy. The reagent was applied for determination of the above mentioned biogenic amines in beverages, and permitted an undemanding separation and determination of the derivatives. Moreover, it is a convenient reagent for analysis of the total amine content by quantitative 19F NMR.

New procedure of selected biogenic amines determination in wine samples by HPLC.

A new procedure for determination of biogenic amines (BA): histamine, phenethylamine, tyramine and tryptamine, based on the derivatization reaction with 2-chloro-1,3-dinitro-5-(trifluoromethyl)-benzene (CNBF), is proposed. The amines derivatives with CNBF were isolated and characterized by X-ray crystallography and (1)H, (13)C, (19)F NMR spectroscopy in solution. The novelty of the procedure is based on the pure and well-characterized products of the amines derivatization reaction. The method was applied for the simultaneous analysis of the above mentioned biogenic amines in wine samples by the reversed phase-high performance liquid chromatography. The procedure revealed correlation coefficients (R(2)) between 0.9997 and 0.9999, and linear range: 0.10-9.00 mg L(-1) (histamine); 0.10-9.36 mg L(-1) (tyramine); 0.09-8.64 mg L(-1) (tryptamine) and 0.10-8.64 mg L(-1) (phenethylamine), whereas accuracy was 97%-102% (recovery test). Detection limit of biogenic amines in wine samples was 0.02-0.03 mg L(-1), whereas quantification limit ranged 0.05-0.10 mg L(-1). The variation coefficients for the analyzed amines ranged between 0.49% and 3.92%. Obtained BA derivatives enhanced separation the analytes on chromatograms due to the inhibition of hydrolysis reaction and the reduction of by-products formation.

Dabigatran vs. low molecular weight heparin in preventing venous thromboembolism after elective hip and knee arthroplasty: evaluation of selected clinical parameters.

One of the most frequently performed surgical procedures in orthopaedy and traumatology are total arthroplasty of the hip and the knee. Patients who are undergoing those treatment are exposed to thromboembolic complications. It is necessary to prevent them against thromboembolic complications. Current standard practice for anticoagulant prophylaxis to prevent venous thromboembolism after total hip or knee arthroplasty includes subcutaneous low-molecular weight heparin. Dabigatran etexilate is an oral, reversible direct thrombin inhibitor, with predictable and reproducible pharmacodynamic effects and pharmacokinetic characteristics that permit once-daily dosing. The aim of this study was to evaluate the incidence of venous thromboembolism (measured using Doppler ultrasonography), pulmonary embolism and mortality after using both types of prophylaxis. Also evaluated the safety of medicines, examining the post-operative blood loss, decreased hematocrit and hemoglobin. We analyzed the incidence of complications by assessing the state of local inflammation, the level of C-reactive protein. There was no significant difference in the safety of the oral and subcutaneous thromboprophylaxis in patients undergoing either total hip or knee replacement. Blood loss after surgery, duration of surgery, decrease of hematocrit and hemoglobin were not significantly different. None of the both drugs did not differ significantly in the incidence of inflammatory complications a systemic and a local. In the studied population, the effectiveness of thromboprophylaxis was high.

Dual stereoselectivity in the dialkylzinc reaction using (-)-beta-pinene derived amino alcohol chiral auxiliaries.

(+)-Nopinone, prepared from naturally occurring (-)-beta-pinene, was converted to the two regioisomeric amino alcohols 3-MAP and 2-MAP in very good yield and excellent isomeric purity. Amino alcohol 3-MAP was synthesized by converting (+)-nopinone to the corresponding alpha-ketooxime. This was reduced to the primary amino alcohol and was converted to the morpholino group through a simple substitution reaction. 3-MAP was characterized by X-ray crystallography, which displayed the rigidity of the pinane framework. Amino alcohol 2-MAP was prepared from its trans isomer 2, which in turn was synthesized via hydroboration/oxidation of the morpholine enamine of (+)-nopinone. Two-dimensional NMR was used to characterize amino alcohol 2-MAP, and NOE was used to confirm its relative stereochemistry. These amino alcohols were employed as chiral auxiliaries in the addition of diethylzinc to benzaldehyde to obtain near-quantitative asymmetric induction in the products. The use of 3-MAP yielded (S)-phenylpropanol in 99% ee, and its regioisomer 2-MAP gave the opposite enantiomer, (R)-phenylpropanol, also in 99% ee. Other aromatic, aliphatic, and alpha,beta-unsaturated aldehydes were implemented in this method, affording secondary alcohols in high yield and enantiomeric excess. Amino alcohols 2-MAP and 3-MAP were also found to be useful in the dimethylzinc addition reaction, both catalyzing the addition to benzaldehyde with nearly quantitative ee. Regioisomeric amino alcohols 2-MAP and 3-MAP, even though they were prepared from one enantiomer of nopinone, provide antipodal enantiofacial selectivity in the dialkylzinc addition reaction. This circumvents the necessity to synthesize amino alcohols derived from (-)-nopinone, which in turn requires the unnatural (+)-beta-pinene. Possible mechanistic insights are offered to explain the dual stereoselectivity observed in the diethylzinc addition reaction involving regioisomeric, pseudo-enantiomeric amino alcohols 3-MAP and 2-MAP.

Lewis acid-catalyzed one-pot, three-component route to chiral 3,3'-bipyrroles.

3,3'-Bipyrroles 3 could be synthesized using a double Michael addition reaction involving diaroyl acetylene 1 and the appropriate 1,3-dicarbonyls 2 using ammonium acetate as a nitrogen source. The axial chirality of bipyrrole was anticipated from the X-ray crystal structure and DFT calculations and confirmed by separating the racemates on a chiral column and subsequent CD spectra of the enantiomers. The absolute configuration of the enantiomers was achieved by theoretical CD spectra calculation using the ZINDO method.

Penetration of a selected antibiotic and antiseptic into a biofilm formed on orthopedic steel implants.

BACKGROUND: The aim of the study was to determine the impact of octenidine hydrochloride and gentamicin on bacterial survival and reduction of biofilms formed on orthopaedic metal implants. MATERIAL AND METHODS: We studied metal orthopaedic components (screws, nails, fragments of wires used in Ilizarov devices) and a bone sequester. The presence and intensity of biofilm formation on the medical biomaterials was determined using the method of Richards et al. by visual evaluation of 2,3,5-triphenyl tetrazolium chloride (TTC) reduction by viable bacteria. The presence and structure of the biofilm on the components of the Ilizarov device, screws and bone sequester was also studied by electron microscopy. Bacterial survival in the biofilm following exposure to the antibiotic and antiseptic was studied by CLSI microdilution method in microtitre plates using TTC. Results. Most of the 16 strains (S. aureus, S. epidermidis, E. coli, Enterobacter) isolated from orthopaedic implants were able to form a biofilm. Established biofilms were resistant to gentamicin and octenidine hydrochloride but demonstrated greater susceptibility to octenidine. CONCLUSIONS: The results of the study indicate that octenidine hydrochloride is more effective than gentamicin in the treatment of infections associated with the formation of a biofilm on orthopaedic implants.