Using Bioelements Isotope Ratios and Fatty Acid Composition to Deduce Beef Origin and Zebu Feeding Regime in Cameroon

The purpose of this study was to address the lack of knowledge regarding the stable isotopic composition of beef from zebu cattle reared in tropical Africa. Sixty beef carcasses belonging to the most common zebu breeds (Goudali, white Fulani, and red Mbororo) were selected and classified according to their subcutaneous fat color (white, cream or yellow). The stable isotope ratios of five bioelements—H, O, C, N, and S—in muscle fractions and the fatty acids composition were analyzed. Zebu meat from Cameroon shows peculiar δ¹³C values, related to the almost exclusive intake of grazed tropical grasses with photosynthetic cycle C4. It also shows δ²H and δ¹⁸O values higher than those reported in other areas of the world and correlated with the isotopic composition of animal drinking water. The white subcutaneous fat (“white type”) zebu showed higher δ²H and lower δ¹³C than the “yellow type”, that is correlated with a higher content of polyunsaturated fatty acid (PUFA) and a lower amount of saturated fatty acid (SFA) and monounsaturated fatty acid (MUFA). Multielement analysis seems to provide promising results for tracing the regional origin of Cameroon beef and some aspects of the livestock system, such as the nutritional status of the animals.     

Essential Oil Composition and Stable Isotope Profile of Cultivated Ocimum campechianum Mill. (Lamiaceae) from Peru

Ocimum campechianum Mill. (Peruvian basil) is an essential oil-bearing plant of the Lamiaceae family. Volatile oil produced through steam distillation of Peruvian basil was examined to establish the aromatic and stable isotope profiles of samples (n = 9) from three different cultivated plots in Peru. The resulting essential oils were analyzed by GC/FID, GC/MS, and GC/IRMS. In accordance with findings from other researchers, multiple chemotypes, defined by the most abundant aromatic compounds, exist within these populations. Overall, 55% of samples are the eugenol chemotype (values ranging 15.4–30.2%), 33% are the methyl eugenol chemotype (values ranging 68.1–68.7%), and a single sample is a mixture of both chemotypes, containing high levels of both eugenol (38.1%) and methyl eugenol (8.6%). Stable isotope ratios, δ²H and δ¹³C, performed on prominent compounds provide supporting data for distinguishing chemotypes. Complete aromatic profiles, stable isotope ratios, and essential oil yield are established for each sample. This study confirms the existence of multiple chemotypes and, for the first time, to the author’s best knowledge, establishes stable isotope ratios for O. campechianum essential oil, which proves a useful tool in further investigating plant metabolism and determining essential oil authenticity.     

Tuning π-Acceptor/σ-Donor Ratio of the 2-Isocyanoazulene Ligand: Non-Fluorinated Rival of Pentafluorophenyl Isocyanide and Trifluorovinyl Isocyanide Discovered

Isocyanoazulenes (CNAz) constitute a relatively new class of isocyanoarenes that offers rich structural and electronic diversification of the organic isocyanide ligand platform. This article considers a series of 2-isocyano-1,3-X₂-azulene ligands (X = H, Me, CO₂Et, Br, and CN) and the corresponding zero-valent complexes thereof, [(OC)₅Cr(2-isocyano-1,3-X₂-azulene)]. Air- and thermally stable, X-ray structurally characterized 2-isocyano-1,3-dimethylazulene may be viewed as a non-benzenoid aromatic congener of 2,6-dimethyphenyl isocyanide (2,6-xylyl isocyanide), a longtime “workhorse” aryl isocyanide ligand in coordination chemistry. Single crystal X-ray crystallographic {Cr–CNAz bond distances}, cyclic voltametric {E_1/2(Cr^0/1+)}, ¹³C NMR {δ(¹³CN), δ(¹³CO)}, UV-vis {dπ(Cr) → pπ*(CNAz) Metal-to-Ligand Charge Transfer}, and FTIR {ν_N≡C, ν_C≡O, k_C≡O} analyses of the [(OC)₅Cr(2-isocyano-1,3-X₂-azulene)] complexes provided a multifaceted, quantitative assessment of the π-acceptor/σ-donor characteristics of the above five 2-isocyanoazulenes. In particular, the following inverse linear relationships were documented: δ(¹³CO_trans) vs. δ(¹³CN), δ(¹³CO_cis) vs. δ(¹³CN), and δ(¹³CO_trans) vs. k_C≡O,trans force constant. Remarkably, the net electron withdrawing capability of the 2-isocyano-1,3-dicyanoazulene ligand rivals those of perfluorinated isocyanides CNC₆F₅ and CNC₂F₃.     

Investigating Hydrogen Isotope Variation during Heating of n-Alkanes under Limited Oxygen Conditions: Implications for Palaeoclimate Reconstruction in Archaeological Settings

This paper reports on a series of heating experiments that focus on n-alkanes extracted from leaf, bark, and xylem tissues of the Celtis australis plant. These lipid biomarkers were analysed for their compound-specific hydrogen isotopic composition (δ²H_wax) under limited oxygen conditions at 150, 250, 350, and 450 °C. Our results reveal isotopic variations in wax lipids of different plant organs during short-term low-temperature combustion. We conclude that, in the absence of a detailed characterisation of the depositional environment in advance of sampling, δ²H_wax values in archaeological or otherwise highly anthropogenic environments should be interpreted cautiously. In addition, we observed that variation in δ²H_wax of leaves is minimal at temperatures ≤ 350 °C, highlighting the potential for δ²H_wax in thermally altered combustion substrates to yield palaeoclimate information, which could allow researchers to investigate links between archaeological and climatic records at a high spatial and temporal resolution.     

Stable Carbon Isotope Analysis of Hexachlorocyclohexanes by Liquid–Liquid Extraction Gas Chromatography Isotope Ratio Mass Spectrometry: Method Evaluation and Applications

Compound specific isotope analysis (CSIA) and enantiomer specific isotope analysis (ESIA) are powerful tools for assessing the fate of hexachlorocyclohexanes (HCHs) in the environment. However, there is no systematic study on the CSIA and ESIA analysis test methods of the carbon isotopes of HCHs in water and soil environments, in particular the isotope fractionation in the pre-concentration process. We endeavored to test the compatibility of CSIA and ESIA with the liquid–liquid extraction method of HCHs in water. The results showed that there were negligible changes in the δ¹³C of HCHs after extraction, indicating that liquid–liquid extraction can be used as a pre-concentration method for the determination of δ¹³C of HCHs in water. The optimized method was validated and then applied to differentiate three HCHs from different manufacturers, to identify in situ degradation of HCHs of groundwater from a contaminated site and to resolve the carbon isotope fractionation occurring in the α-HCH oxidation by CaO₂/Fe(II) Fenton system. The results showed that the same reagents from different manufacturers have different carbon isotope compositions, and different isomers from the same manufacturer also have different isotope compositions, showing useful evidence in identifying the source of HCHs. The more enriched δ¹³C in the down-gradient wells indicated that HCHs have undergone biodegradation or/and chemical reactions in the groundwater system of the site. Carbon isotopic enrichment factors (ε_C) of −1.90 ± 0.10‰ were obtained in the oxidation process. Hence, the method validated in this study has great potential as a method for identifying the degradation of HCHs in a water environment.     

Traceability and Authentication of Manila Clams from North-Western Adriatic Lagoons Using C and N Stable Isotope Analysis

In the Adriatic lagoons of northern Italy, manila clam (Ruditapes philippinarum) farming provides important socio-economic returns and local clams should be registered with the Protected Designations of Origin scheme. Therefore, there is a need for the development of rapid, cost-effective tests to guarantee the origin of the product and to prevent potential fraud. In this work, an elemental analysis (EA) coupled with isotope ratio mass spectrometry (IRMS) was employed to identify the isotopic fingerprints of clams directly collected onsite in three Adriatic lagoons and bought at a local supermarket, where they exhibited certification. In particular, a multivariate analysis of C/N, δ¹³C and δ¹⁵N in manila clam tissues as well as δ¹³C in shells and Δ¹³C (calculated as δ¹³C_shell–δ¹³C_tissues) seems a promising approach for tracking the geographical origin of manila clams at the regional scale.     

Authentication of Iranian Saffron (Crocus sativus) Using Stable Isotopes δ13C and δ2H and Metabolites Quantification

Saffron is a very high value-added ingredient used in the food supplement market and contains a high level of safranal. Adding synthetic safranal to saffron, which is significantly cheaper, and falsifying the origin of saffron may represent recurrent fraud. Saffron from different countries was analyzed to determine the stable isotope ratios δ¹³C and δ²H from safranal by gas chromatography coupled with isotope-ratio mass spectrometry (GC-C/P-IRMS) and the concentration of saffron metabolites with ultra-high performance liquid chromatography coupled with diode array detector (UHPLC-DAD). The isotopic analysis highlighted a higher ratio of δ²H in synthetic safranal than in natural safranal; the mean values were 36‰ (+/− 40) and −210‰ (+/− 35), respectively. The δ¹³C between Iranian, Spanish and other saffron was significantly different and represents median values of −28.62‰, −30.12‰ and −30.70‰, respectively. Moreover, linear and quadratic discriminant analyses (LDA and QDA) were computed using the two isotope ratios of safranal and the saffron metabolites. A first QDA showed that trans-crocetin and the δ¹³C of safranal, picrocrocin, and crocin C3 concentrations clearly differentiated Iranian saffron from other origins. A second model identified δ¹³C, trans-crocetin, crocin C2, crocin C3, and picrocrocin as good predictors to discriminate saffron samples from Iran, Spain, or other origins, with a total ability score classification matrix of 100% and a prediction matrix of 82.5%. This combined approach may be a useful tool to authenticate the origin of unknown saffron.     

N-phenyl-6-chloro-4-hydroxy-2-quinolone-3-carboxamides: Molecular Docking,Synthesis, and Biological Investigation as Anticancer Agents

Cancer is a multifactorial disease and the second leading cause of death worldwide. Diverse factors induce carcinogenesis, such as diet, smoking, radiation, and genetic defects. The phosphatidylinositol 3-kinase (PI3Kα) has emerged as an attractive target for anticancer drug design. Eighteen derivatives of N-phenyl-6-chloro-4-hydroxy-2-quinolone-3-carboxamide were synthesized and characterized using FT-IR, NMR (¹H and ¹³C), and high-resolution mass spectra (HRMS). The series exhibited distinct antiproliferative activity (IC₅₀ µM) against human epithelial colorectal adenocarcinoma (Caco-2) and colon carcinoma (HCT-116) cell lines, respectively: compounds 16 (37.4, 8.9 µM), 18 (50.9, 3.3 µM), 19 (17.0, 5.3 µM), and 21 (18.9, 4.9 µM). The induced-fit docking (IFD) studies against PI3Kαs showed that the derivatives occupy the PI3Kα binding site and engage with key binding residues.     

Neuropeltis acuminata (P. Beauv.): Investigation of the Chemical Variability and In Vitro Anti-inflammatory Activity of the Leaf Essential Oil from the Ivorian Species

The variability of chemical composition of the leaf essential oil (EO) from Neuropeltis acuminata, a climbing liana growing wild in Ivory Coast, was investigated for the first time. The in vitro anti-inflammatory activity was also evaluated. Thirty oil samples were isolated from leaves collected in three forests of the country and analyzed using a combination of Column Chromatography (CC), Gas Chromatography with Retention Indices (GC(FID)), Gas Chromatography-Mass Spectrometry (GC-MS), and ¹³Carbon-Nuclear Magnetic Resonance (¹³C-NMR). Fractionation by CC led to the first-time isolation from natural source of δ-cadinen-11-ol, whose structural elucidation by one dimension (1D) and 2D-NMR spectroscopy is reported here. Finally, 103 constituents accounting for 95.7 to 99.6% of the samples’ compositions were identified. As significant variations of the major constituents were observed, the 30 oil compositions were submitted to hierarchical cluster and principal components analyses. Five distinct groups were evidenced: Group I, dominated by (E)-β-caryophyllene, kessane, and δ-cadinene, while the main constituents of Group II were germacrene B, ledol, α-humulene, (E)-γ-bisabolen-12-ol, and γ-elemene. Group III exhibited guaiol, germacrene D, atractylone, (E)-γ-bisabolen-12-ol, δ-cadinene and bulnesol as main compounds. Group IV was dominated by (E)-nerolidol, guaiol, selina-4(15),7(11)-diene and bulnesol, whereas (E)-β-caryophyllene, α-humulene and α-muurolene were the prevalent compounds of Group V. As the harvest took place in the same dry season in the three forests, the observed chemical variability could be related to harvest sites, which includes climatic and pedologic factors, although genetic factors could not be excluded. The leaf oil sample S24 behaved as a high inhibitor of LipOXygenase (LOX) activity (half maximum Inhibitory Concentration, IC₅₀: 0.059 ± 0.001 mg mL⁻¹), suggesting an anti-inflammatory potential.     

Dinuclear Lanthanide(III) Complexes from the Use of Methyl 2-Pyridyl Ketoxime: Synthetic,Structural, and Physical Studies

The first use of methyl 2-pyridyl ketoxime (mepaoH) in homometallic lanthanide(III) [Ln(III)] chemistry is described. The 1:2 reactions of Ln(NO₃)₃·nH₂O (Ln = Nd, Eu, Gd, Tb, Dy; n = 5, 6) and mepaoH in MeCN have provided access to complexes [Ln₂(O₂CMe)₄(NO₃)₂(mepaoH)₂] (Ln = Nd, 1; Ln = Eu, 2; Ln = Gd, 3; Ln = Tb, 4; Ln = Dy, 5); the acetato ligands derive from the Ln^III—mediated hydrolysis of MeCN. The 1:1 and 1:2 reactions between Dy(O₂CMe)₃·4H₂O and mepaoH in MeOH/MeCN led to the all-acetato complex [Dy₂(O₂CMe)₆(mepaoH)₂] (6). Treatment of 6 with one equivalent of HNO₃ gave 5. The structures of 1, 5, and 6 were solved by single-crystal X-ray crystallography. Elemental analyses and IR spectroscopy provide strong evidence that 2–4 display similar structural characteristics with 1 and 5. The structures of 1–5 consist of dinuclear molecules in which the two Ln^III centers are bridged by two bidentate bridging (η¹:η¹:μ₂) and two chelating-bridging (η¹:η²:μ₂) acetate groups. The Ln^III atoms are each chelated by a N,N’-bidentate mepaoH ligand and a near-symmetrical bidentate nitrato group. The molecular structure of 6 is similar to that of 5, the main difference being the presence of two chelating acetato groups in the former instead of the two chelating nitrato groups in the latter. The geometry of the 9-coordinate Ln^III centers in 1, 5 and 6 can be best described as a muffin-type (MFF-9). The 3D lattices of the isomorphous 1 and 5 are built through H-bonding, π⋯π stacking and C-H⋯π interactions, while the 3D architecture of 6 is stabilized by H bonds. The IR spectra of the complexes are discussed in terms of the coordination modes of the organic and inorganic ligands involved. The Eu(III) complex 2 displays a red, metal-ion centered emission in the solid state; the Tb^III atom in solid 4 emits light in the same region with the ligand. Magnetic susceptibility studies in the 2.0–300 K range reveal weak antiferromagnetic intramolecular Gd^III…Gd^III exchange interactions in 3; the J value is −0.09(1) cm⁻¹ based on the spin Hamiltonian Ĥ = −J(Ŝ_Gd1·Ŝ_Gd2).     

Synthesis of [18F]F-γ-T-3, a Redox-Silent γ-Tocotrienol (γ-T-3) Vitamin E Analogue for Image-Based In Vivo Studies of Vitamin E Biodistribution and Dynamics

Vitamin E, a natural antioxidant, is of interest to scientists, health care pundits and faddists; its nutritional and biomedical attributes may be validated, anecdotal or fantasy. Vitamin E is a mixture of tocopherols (TPs) and tocotrienols (T-3s), each class having four substitutional isomers (α-, β-, γ-, δ-). Vitamin E analogues attain only low concentrations in most tissues, necessitating exacting invasive techniques for analytical research. Quantitative positron emission tomography (PET) with an F-18-labeled molecular probe would expedite access to Vitamin E’s biodistributions and pharmacokinetics via non-invasive temporal imaging. (R)-6-(3-[¹⁸F]Fluoropropoxy)-2,7,8-trimethyl-2-(4,8,12-trimethyltrideca-3,7,11-trien-1-yl)-chromane ([¹⁸F]F-γ-T-3) was prepared for this purpose. [¹⁸F]F-γ-T-3 was synthesized from γ-T-3 in two steps: (i) 1,3-di-O-tosylpropane was introduced at C6-O to form TsO-γ-T-3, and (ii) reaction of this tosylate with [¹⁸F]fluoride in DMF/K₂₂₂. Non-radioactive F-γ-T-3 was synthesized by reaction of γ-T-3 with 3-fluoropropyl methanesulfonate. [¹⁸F]F-γ-T-3 biodistribution in a murine tumor model was imaged using a small-animal PET scanner. F-γ-T-3 was prepared in 61% chemical yield. [¹⁸F]F-γ-T-3 was synthesized in acceptable radiochemical yield (RCY 12%) with high radiochemical purity (>99% RCP) in 45 min. Preliminary F-18 PET images in mice showed upper abdominal accumulation with evidence of renal clearance, only low concentrations in the thorax (lung/heart) and head, and rapid clearance from blood. [¹⁸F]F-γ-T-3 shows promise as an F-18 PET tracer for detailed in vivo studies of Vitamin E. The labeling procedure provides acceptable RCY, high RCP and pertinence to all eight Vitamin E analogues.     

Guaianolide Sesquiterpene Lactones from Centaurothamnus maximus

Centaurothamnus maximus (family Asteraceae), is a leafy shrub indigenous to the southwestern Arabian Peninsula. With a paucity of phytochemical data on this species, we set out to chemically characterize the plant. From the aerial parts, two newly identified guaianolides were isolated: 3β-hydroxy-4α(acetoxy)-4β(hydroxymethyl)-8α-(4-hydroxy methacrylate)-1αH,5αH, 6αH-gual-10(14),11(13)-dien-6,12-olide (1) and 15-descarboxy picrolide A (2). Seven previously reported compounds were also isolated: 3β, 4α, 8α-trihydroxy-4-(hydroxymethyl)-lαH, 5αH, 6βH, 7αH-guai-10(14),11(13)-dien-6,12-olide (3), chlorohyssopifolin B (4), cynaropikrin (5), hydroxyjanerin (6), chlorojanerin (7), isorhamnetin (8), and quercetagetin-3,6-dimethyl ether-4’-O-β-d-pyranoglucoside (9). Chemical structures were elucidated using spectroscopic techniques, including High Resolution Fast Atom Bombardment Mass Spectrometry (HR-FAB-MS), 1D NMR; ¹H, ¹³C NMR, Distortionless Enhancement by Polarization Transfer (DEPT), and 2D NMR (¹H-¹H COSY, HMQC, HMBC) analyses. In addition, a biosynthetic pathway for compounds 1–9 is proposed. The chemotaxonomic significance of the reported sesquiterpenoids and flavonoids considering reports from other Centaurea species is examined.     

Molecular Environment Effects That Modulate the Photophysical Properties of Novel 1,3-Phosphinoamines Based on 2,1,3-Benzothiadiazole

We report synthesis, crystal structure, and photophysical properties of novel 1,3-phosphinoamines based on 4-amino-2,1,3-benzothiadiazole (NH₂-btd): Ph₂PCH(Ph)NH-btd (1) and Ph₂P(E)CH(Ph)NH-btd, (E = O (2α and 2β·thf), S (3), Se (4)). Chalcogenides 2–4 exhibit bright emissions with a major band at 519–536 nm and a minor band at 840 nm. According to TD-DFT calculations, the first band is attributed to fluorescence, while the second band corresponds to phosphorescence. In the solid state, room temperature quantum yield reaches 93% in the case of the sulphide. The compounds under study feature effects of the molecular environment on the luminescent properties, which manifest themselves in fluorosolvatochromism as well as in a luminescent response to changes in crystal packing and in contributions to aggregation effects. Specifically, transformation of solid 2β·thf to solvate-free 2β either by aging or by grinding causes crystal packing changes, and, as a result, a hypsochromic shift of the emission band. Polystyrene films doped with 2 reveal a bathochromic shift upon increasing the mass fraction from 0.2 to 3.3%, which is caused by molecular aggregation effects.     

Chemical Variability and In Vitro Anti-Inflammatory Activity of Leaf Essential Oil from Ivorian Isolona dewevrei (De Wild. & T. Durand) Engl. & Diels

The chemical variability and the in vitro anti-inflammatory activity of the leaf essential oil from Ivorian Isolona dewevrei were investigated for the first time. Forty-seven oil samples were analyzed using a combination of CC, GC(RI), GC-MS and ¹³C-NMR, thus leading to the identification of 113 constituents (90.8–98.9%). As the main components varied drastically from sample to sample, the 47 oil compositions were submitted to hierarchical cluster and principal components analyses. Three distinct groups, each divided into two subgroups, were evidenced. Subgroup I−A was dominated by (Z)-β-ocimene, β-eudesmol, germacrene D and (E)-β-ocimene, while (10βH)-1β,8β-oxido-cadina-4-ene, santalenone, trans-α-bergamotene and trans-β-bergamotene were the main compounds of Subgroup I−B. The prevalent constituents of Subgroup II−A were germacrene B, (E)-β-caryophyllene, (5αH,10βMe)-6,12-oxido-elema-1,3,6,11(12)-tetraene and γ-elemene. Subgroup II−B displayed germacrene B, germacrene D and (Z)-β-ocimene as the majority compounds. Germacrene D was the most abundant constituent of Group III, followed in Subgroup III−A by (E)-β-caryophyllene, (10βH)-1β,8β-oxido-cadina-4-ene, germacrene D-8-one, and then in Subgroup III−B by (Z)-β-ocimene and (E)-β-ocimene. The observed qualitative and quantitative chemical variability was probably due to combined factors, mostly phenology and season, then harvest site to a lesser extent. The lipoxygenase inhibition by a leaf oil sample was also evaluated. The oil IC₅₀ (0.020 ± 0.005 mg/mL) was slightly higher than the non-competitive lipoxygenase inhibitor NDGA IC₅₀ (0.013 ± 0.003 mg/mL), suggesting a significant in vitro anti-inflammatory potential.     

Structural Elucidation of the O-Antigen Polysaccharide from Escherichia coli O181

Shiga-toxin-producing Escherichia coli (STEC) is an important pathogen associated to food-borne infection in humans; strains of E. coli O181, isolated from human cases of diarrhea, have been classified as belonging to this pathotype. Herein, the structure of the O-antigen polysaccharide (PS) from E. coli O181 has been investigated. The sugar analysis showed quinovosamine (QuiN), glucosamine (GlcN), galactosamine (GalN), and glucose (Glc) as major components. Analysis of the high-resolution mass spectrum of the oligosaccharide (OS), obtained by dephosphorylation of the O-deacetylated PS with aqueous 48 % hydrofluoric acid, revealed a pentasaccharide composed of two QuiNAc, one GlcNAc, one GalNAc, and one Glc residue. The ¹H and ¹³C NMR chemical shift assignments of the OS were carried out using 1 D and 2 D NMR experiments, and the OS was sequenced using a combination of tandem mass spectrometry (MS/MS) data and NMR ¹³C NMR glycosylation shifts. The structure of the native PS was determined using NMR spectroscopy, and it consists of branched pentasaccharide repeating units joined by phosphodiester linkages: →4)[α-l-QuipNAc-(1→3)]-α-d-GalpNAc6Ac-(1→6)-α-d-Glcp-(1→P-4)-α-l-QuipNAc-(1→3)-β-d-GlcpNAc-(1→; the O-acetyl groups represent 0.4 equivalents per repeating unit. Both the OS and PSs exhibit rare conformational behavior since two of the five anomeric proton resonances could only be observed at an elevated temperature.     

Application of diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) for the identification of potential diagenesis and crystallinity changes in teeth

During burial, diagenetic alteration can invalidate the paleodietary signature, which the hydroxyapatite (Ca₅(PO₄)₃OH) matrix in incremental tissues, such as tooth enamel, provides. Thus, analytical methods that can evaluate diagenetic changes are crucial in anthropological and archaeological investigations. Modern deciduous tooth enamel (exfoliated) from Solis, Mexico and Kalama, Egypt, as well as Bronze Age (circa 2200 B.C.E.) adult enamel from (present-day) Tell Abraq, U.A.E. and adult enamel from the New York African Burial Ground (NYABG) in lower Manhattan, were analyzed using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The samples were compared to synthetic hydroxyapatite powder and bone ash samples. The DRIFTS spectra of tooth enamel yielded similar infra red finger print pattern to previous pellet-based FTIR spectra in both absorbance and Kubelka–Munk units. The study demonstrates that DRIFTS is a convenient alternative to pellet-based transmission FTIR in testing diagenetic changes in hard tissue for archaeological investigations. Tooth enamel samples contained a higher carbonate–phosphate ratio than synthetic hydroxyapatite and bone ash standard samples. Correlations are reported between Crystallinity Index (CI_Ab) and carbonate–phosphate ratio, strontium–calcium ratio, and fluoride peak appearance. Crystallinity indexes (CI_Ab) were in the range of 2.6–3.8 (in absorbance units) and Kubelka–Munk Crystallinity indexes (CI_KM) were in the range of 3.1–4.9.     

Fatty Acid Analysis,Chemical Constituents,Biological Activity and Pesticide Residues Screening in Jordanian Propolis

Propolis is a resinous natural product collected by honeybees (Apis mellifera and others) from tree exudates that has been widely used in folk medicine. The present study was carried out to investigate the fatty acid composition, chemical constituents, antioxidant, and xanthine oxidase (XO) inhibitory activity of Jordanian propolis, collected from Al-Ghour, Jordan. The hexane extract of Jordanian propolis contained different fatty acids, which are reported for the first time by using GC-FID. The HPLC was carried out to identify important chemical constituents such as fatty acids, polyphenols and α-tocopherol. The antioxidant and xanthine oxidase inhibitory activities were also monitored. The major fatty acid identified were palmitic acid (44.6%), oleic acid (18:1∆⁹cis, 24.6%), arachidic acid (7.4%), stearic acid (5.4%), linoleic acid (18:2∆^9–12cis, 3.1%), caprylic acid (2.9%), lignoceric acid (2.6%), cis-11,14-eicosaldienoic acid (20:2∆^11–14cis, 2.4%), palmitoleic acid (1.5%), cis-11-eicosenoic acid (1.2%), α–linolenic acid (18:3∆^9–12–15cis, 1.1%), cis-13,16-docosadienoic acid (22:2∆^13–16cis, 1.0%), along with other fatty acids. The major chemical constituents identified using gradient HPLC-PDA analysis were pinocembrin (2.82%), chrysin (1.83%), luteolin-7-O-glucoside (1.23%), caffeic acid (1.12%), caffeic acid phenethyl ester (CAPE, 0.79%), apigenin (0.54%), galangin (0.46%), and luteolin (0.30%); while the minor constituents were hesperidin, quercetin, rutin, and vanillic acid. The percentage of α-tocopherol was 2.01 µg/g of the lipid fraction of propolis. Antioxidant properties of the extracts were determined via DPPH radical scavenging. The DPPH radical scavenging activities (IC₅₀) of different extracts ranged from 6.13 to 60.5 µg/mL compared to ascorbic acid (1.21 µg/mL). The xanthine oxidase inhibition (IC₅₀) ranged from 75.11 to 250.74 µg/mL compared to allopurinol (0.38 µg/mL). The results indicate that the various flavonoids, phenolic compounds, α-tocopherol, and other constituents which are present in propolis are responsible for the antioxidant and xanthine oxidation inhibition activity. To evaluate the safety studies of propolis, the pesticide residues were also monitored by LC-MS-MS 4500 Q-Trap. Trace amounts of pesticide residue (ng/mL) were detected in the samples, which are far below the permissible limit as per international guidelines.     

Arene Ruthenium(II) Complexes Bearing the κ-P or κ-P,κ-S Ph2P(CH2)3SPh Ligand

Neutral [Ru(η⁶-arene)Cl₂{Ph₂P(CH₂)₃SPh-κP}] (arene = benzene, indane, 1,2,3,4-tetrahydronaphthalene: 2a, 2c and 2d) and cationic [Ru(η⁶-arene)Cl(Ph₂P(CH₂)₃SPh-κP,κS)]X complexes (arene = mesitylene, 1,4-dihydronaphthalene; X = Cl: 3b, 3e; arene = benzene, mesitylene, indane, 1,2,3,4-tetrahydronaphthalene, and 1,4-dihydronaphthalene; X = PF₆: 4a–4e) complexes were prepared and characterized by elemental analysis, IR, ¹H, ¹³C and ³¹P NMR spectroscopy and also by single-crystal X-ray diffraction analyses. The stability of the complexes has been investigated in DMSO. Complexes have been assessed for their cytotoxic activity against 518A2, 8505C, A253, MCF-7 and SW480 cell lines. Generally, complexes exhibited activity in the lower micromolar range; moreover, they are found to be more active than cisplatin. For the most active ruthenium(II) complex, 4b, bearing mesitylene as ligand, the mechanism of action against 8505C cisplatin resistant cell line was determined. Complex 4b induced apoptosis accompanied by caspase activation.     

Isotopic Characterization of 100% Agave Tequila (Silver,Aged and Extra-Aged Class) for Its Use as an Additional Parameter in the Determination of the Authenticity of the Beverage Maturation Time

Isotopic ratios of δ¹³C_VPDB and δ¹⁸O_VSMOW have been used as an additional parameter to ensure the authenticity of the aging time of 100% agave tequila. For this purpose, 120 samples were isotopically analyzed (40 silver class, 40 aged class, and 40 extra-aged classes). The samples were obtained through a stratified sampling by proportional allocation, considering tequila producers from the main different regions of Jalisco, Mexico (Valles 41%, Altos Sur 31%, Cienega 16%, and Centro 12%). The results showed that the δ¹³C_VPDB was found in an average of −12.85 ‰ for all the analyzed beverages, with no significant difference between them. Since for all the tested samples the Agave tequilana Weber blue variety was used as source of sugar to obtain alcohol, those results were foreseeable, and confirm the origin of the sugar source. Instead, the results for δ¹⁸O_VSMOW showed a positive slope linear trend for the aging time (silver class 19.52‰, aged class 20.54‰, extra-aged class 21.45‰), which is associated with the maturation process, there are oxidation reactions that add congeneric compounds to the beverage, these can be used as tracers for the authenticity of the aging time. Additionally, the experimental data showed homogeneity in the beverages regardless of the production region, evidencing the tequila industry’s high-quality standards. However, a particular case occurs with the δ¹⁸O_VSMOW data for the silver class samples, in which a clear trend is noted with the altitude of the region of origin; therefore, this information suggests that this analytical parameter could be useful to authenticate the regional origin of beverage.     

Isotopic Traceability (13C and 18O) of Greek Olive Oil

In recent years, isotopic analysis has been proven a valuable tool for the determination of the origin of various materials. In this article, we studied the ¹⁸O and ¹³C isotopic values of 210 olive oil samples that were originated from different regions in Greece in order to verify how these values are affected by the climate regime. We observed that the δ¹⁸O isotopic values range from 19.2 ‰ to 25.2 ‰ and the δ¹³C values range from −32.7 ‰ to −28.3 ‰. These differences between the olive oils’ isotopic values depended on the regional temperature, the meteoric water, and the distance from the sea. Furthermore, we studied the ¹³C isotopic values of biophenolic extracts, and we observed that they have same capability to differentiate the geographic origin. Finally, we compared the isotopic values of Greek olive oils with samples from Italy, and we concluded that there is a great dependence of oxygen isotopes on the climatic characteristics of the different geographical areas.