Combination of capillary GC, GC/MS and13C-NMR for the characterization of the rhizome oil ofPiper betleL. (Piperaceae) from Vietnam

The essential oil from the rhizomes ofPiper betleL. (betel), collected around Hue, was obtained in 0.20% yield. The oil was examined by a combination of capillary GC and GC/MS.13C-NMR studies confirmed the structure assignments proposed by retention data and mass spectra of the components with a content higher than 1%. In some instances the structure elucidation based on GC and GC/MS data had to be corrected. More than forty constituents were found of which the major ones were α-cadinol (26.2%), δ-cadinene (11.7%), and about equal amounts of T-cadinol and T-muurolol (unseparated, together 20.7%). This study clearly illustrates the advantage of complementary identification techniques.

Download Full-text

Characterization of Cerebral Glutamine Uptake from Blood in the Mouse Brain: Implications for Metabolic Modeling of 13C NMR Data

Journal of Cerebral Blood Flow & Metabolism ◽

10.1038/jcbfm.2014.129 ◽

2014 ◽

Vol 34 (10) ◽

pp. 1666-1672 ◽

Cited By ~ 19

Author(s):

Puneet Bagga ◽

Kevin L Behar ◽

Graeme F Mason ◽

Henk M De Feyter ◽

Douglas L Rothman ◽

...

Keyword(s):

Ex Vivo ◽

Metabolic Model ◽

Synthesis Rate ◽

Nmr Studies ◽

Nmr Data ◽

Glutamine Synthesis ◽

Time Courses ◽

Glutamine Uptake ◽

C Nmr

13C Nuclear Magnetic Resonance (NMR) studies of rodent and human brain using [1-13C]/[1,6-13C2]glucose as labeled substrate have consistently found a lower enrichment (~25% to 30%) of glutamine-C4 compared with glutamate-C4 at isotopic steady state. The source of this isotope dilution has not been established experimentally but may potentially arise either from blood/brain exchange of glutamine or from metabolism of unlabeled substrates in astrocytes, where glutamine synthesis occurs. In this study, the contribution of the former was evaluated ex vivo using 1H-[13C]-NMR spectroscopy together with intravenous infusion of [U-13C5]glutamine for 3, 15, 30, and 60 minutes in mice. 13C labeling of brain glutamine was found to be saturated at plasma glutamine levels > 1.0 mmol/L. Fitting a blood–astrocyte–neuron metabolic model to the 13C enrichment time courses of glutamate and glutamine yielded the value of glutamine influx, VGln(in), 0.036 ± 0.002 μmol/g per minute for plasma glutamine of 1.8 mmol/L. For physiologic plasma glutamine level (~0.6 mmol/L), VGln(in) would be ~0.010 μmol/g per minute, which corresponds to ~6% of the glutamine synthesis rate and rises to ~11% for saturating blood glutamine concentrations. Thus, glutamine influx from blood contributes at most ~20% to the dilution of astroglial glutamine-C4 consistently seen in metabolic studies using [1-13C]glucose.

Download Full-text

Design, preparation and characterization of a new ionic liquid, 1,3-disulfonic acid benzimidazolium chloride, as an efficient and recyclable catalyst for the synthesis of tetrahydropyridine under solvent-free conditions

RSC Advances ◽

10.1039/c5ra10699k ◽

2015 ◽

Vol 5 (83) ◽

pp. 67405-67411 ◽

Cited By ~ 12

Author(s):

Mohsen Abbasi

Keyword(s):

Ionic Liquid ◽

Mass Spectra ◽

Recyclable Catalyst ◽

Solvent Free ◽

Disulfonic Acid ◽

H Nmr ◽

Solvent Free Conditions ◽

Ft Ir ◽

C Nmr

In the present work, 1,3-disulfonic acid benzimidazolium chloride as a new ionic liquid, is synthesized, and characterized by studying its FT-IR, 1H NMR, 13C NMR as well as mass spectra.

Download Full-text

Conversion of Metabolomic Data to Genomic Marker for Genetic Characterization of Piper betle L. Chemotypes: A Review

Agricultural Reviews ◽

10.18805/ag.r-2118 ◽

2021 ◽

Author(s):

Bidisha Mondal

Keyword(s):

Essential Oil ◽

Genomic Analysis ◽

Piper Betle ◽

Germplasm Management ◽

Metabolomic Profiling ◽

Metabolomic Data ◽

Genomic Marker ◽

Unique Trace ◽

Metabolome Profiling

The Indian perfumery industry is shifting towards natural product. In India including West Bengal betel leaves produces high quality essential oil as well contribute to Indian fresh vegetable export. The crop is cultivated from stem cutting and suffers from authenticity problem of cultivars with redundant names. The genetic screening and characterization of cultivars were not initiated due to unavailability of reliable markers. The essential oil metabolomic study identified some polar and non-polar volatile signature compounds. Metabolomic profiling of cultivars is not consistent due to seasonal variation in the production of secondary metabolites and ignorance in marking of unique trace discriminatory compounds. In this paper gene ontogeny study was made on major signature compounds to obtain the complete coding sequence (CDS) of the aroma-genes. The CDS information of aroma-genes could be utilized to construct robust DNA markers to eradicate authentication problem and germplasm management of Piper. The direct genomic analysis could supersede the metabolome profiling. Information available in NCBI, DDBJ and EMBL database were searched for gene ontogeny study utilizing available metabolomic data. The information and method depicted could be efficiently utilized for Piper genomics. Aroma-scientists could apply this technique to validate promising cultivars and competent germplasm management.

Download Full-text

Characterization of Volatile Components of Zingiber roseum Essential Oil Using Capillary GC on Modified Cyclodextrins

Natural Product Communications ◽

10.1177/1934578x1300800223 ◽

2013 ◽

Vol 8 (2) ◽

pp. 1934578X1300800 ◽

Cited By ~ 1

Author(s):

VPPalayam S Pragadheesh ◽

Anju Yadav ◽

Manju Singh ◽

Chandan S Chanotiya

Keyword(s):

Essential Oil ◽

Essential Oils ◽

Enantiomeric Excess ◽

Volatile Components ◽

Capillary Gc ◽

Modified Cyclodextrins ◽

Cyclodextrin Cavity ◽

Possible Cause ◽

Chiral Gas Chromatography

The essential oil from different parts of Zingiber roseum plants was extracted by hydrodistillation, and analyzed using enantio-GC, capillary-GC and GC-MS. Two chiral selectors, 6- tert-butyldimethylsilyl-2,3-diethyl-β-cyclodextrin (TBDE-β-CD), and 2,3,6-methyl-β-cyclodextrin (PM-β-CD) doped into 14% cyanopropylphenyl/ 86% dimethylpolysiloxane, and 35% diphenyl/ 65% dimethylpolysiloxane, respectively were compared in order to clarify the stereochemistry and enantioselectivity of terpenoids using chiral gas chromatography. The enantiomeric excess for (1R)-(+)-α-pinene, (1R)-(+)-β-pinene, and (R)-(+)-limonene were characteristic for the rhizome. In TBDE-β-cyclodextrin coated chiral columns, a significant increase in separation factor (a) for β-pinene, limonene, linalool and α-terpineol enantiomers was observed when compared with methyl substituted β-cyclodextrin. The increase in chain length of the alkyl substituents may be the possible cause for enantiomer separation in β-cyclodextrin cavity. In addition, enantioreversal of α-pinene enantiomers in 6-tert-butyldimethylsilyl-2,3-diethyl-β-cyclodextrin was noticed as a unique feature. The enantiomeric compositions of Z. roseum fruit and flower essential oils were similar, but, in contrast, the rhizome oil contained an entirely different composition. Therefore, these results aid in the authentication of the natural origin of Z. roseum essential oils.

Download Full-text

Preparative Capillary GC for Characterization of Five Dracocephalum Essential Oils from Mongolia, and their Mosquito Larvicidal Activity

Natural Product Communications ◽

10.1177/1934578x1601101030 ◽

2016 ◽

Vol 11 (10) ◽

pp. 1934578X1601101

Author(s):

Gülmira Özek ◽

Nurhayat Tabanca ◽

Mohammed M. Radwan ◽

Sanduin Shatar ◽

Altaa Altantsetseg ◽

...

Keyword(s):

Essential Oils ◽

Larvicidal Activity ◽

System Structure ◽

Capillary Gc ◽

Adulticidal Activity ◽

Fraction Collector ◽

First Time ◽

C Nmr

The chemical composition and mosquito larvicidal and adulticidal activity of five essential oils (EOs), Dracocephalum ruyschiana L. (DR), D. foetidum Bunge (DF), D. moldavica L. (DM), D. fruticulosum Steph. ex Willd. (DFr) and D. peregrinum L. (DP) were evaluated. Simultaneous GC-FID and GC-MS analyses revealed in the EOs of DR, DF and DM an unidentified compound (1) ([M+122], 5.4%, 57.9% and 74.0%, respectively). Therefore, we aimed to isolate compound 1 using Preparative Capillary GC (PCGC) connected to a Preparative Fraction Collector (PFC) system. Structure determination of 1 was determined by 1H- and 13C-NMR as p-mentha-1,8-dien-10-al (1, limonen-10-al). Other detected major constituents were thymol (34.0%) and carvacrol (6.1%) in DR; limonene (28.8%) in DF; cis-chrysanthenol acetate (29.1%) and trans-verbenol (5.0%) in DFr; and linalool (17.9%), trans-β-bergamotene (7.9%), (E)-nerolidol (7.7%) and eugenol (5.5%) in DP. The DFr, DP, DR and DM EOs produced 100% mortality to 1st instar larvae of Aedes aegypti L. at 250 ppm and DR and DM EO exhibited the strongest activity and killed 100% 1st instar larvae at 62.5 ppm. No adulticidal activity was observed against female Ae. aegypti. In the scope of the present study, for the first time isolation of limonen-10-al (1) from DR, DM, and DP EOs and larvicidal activity of five Dracocephalum EOs were reported.

Download Full-text

Ligandenmangelkomplexe des Cadmiums. Synthese und spektroskopische Charakterisierung molekularer (Pentafluorphenyl)cadmium-Thiolate und die Struktur des Cubankomplexes [{Cd(C6F5)(SBut)}4] / Ligand-Deficient Complexes of Cadmium. Synthesis and Spectroscopic Characterization of Molecular Pentafluorophenyl Cadmium Thiolates and the Structure of the Cubane Complex [{Cd(C6F5)(SBut)}4]

Zeitschrift für Naturforschung B ◽

10.1515/znb-1994-0119 ◽

1994 ◽

Vol 49 (1) ◽

pp. 119-127 ◽

Cited By ~ 9

Author(s):

Anne-Kathrin Duhme ◽

Henry Strasdeit

Keyword(s):

Mass Spectra ◽

Spectral Feature ◽

Spectroscopic Characterization ◽

Coupling Constant ◽

Triclinic Space Group ◽

Mean Values ◽

Low Field ◽

Field Shift ◽

C Nmr

Abstract In toluene, bis(pentafluorophenyl)cadmium(II) and thiols RSH (R = But, 2,4,6-Pri3C6H2, 2,4,6-But3C6H2) react to give soluble pentafluorophenyl cadmium thiolates [(Cd(C6F5)(SR)}n] The compounds [{Cd(C6F5)(SBut)}4] (1) ∙ 0.5 C6H5CH3, [ {Cd(C6F5)(SC6H2Pri3-2,4,6)}n ] (2) ∙ ca. 0.25n C6H5CH3, and [{Cd(C6F5)(SC6H2But3-2,4,6)} n] (3) ∙ ca. 0.25 n C6H5CH3 have been prepared in 65, 59 and 78% yield, respectively. 1 ∙ 0.5 C6H5CH3 crystallizes in the triclinic space group P1̄ with a = 11,635(1)Å, b = 11.583(1)Å, c = 21.480(2)Å, α = 82.12(1)°, β = 76.26(1)°, γ = 89.35(1)°, and Z = 2. 1 is a cubane-type complex with a {Cd4(μ3-SBut)4}4+ core. Each Cd atom is coordinated by three bridging thiolato ligands and one terminal C6F5 group (Cd - S 2.62 Å, Cd - C 2.15 Å (mean values)). The central C atoms of the ButS− ligands of 1 show a remarkable low-field shift o f their 13C NMR resonance (12.3 ppm relative to the value of the free thiol). A characteristic spectral feature of (Cd(C6F5) }+ complexes is the large value of the coupling constant 2J (19F ,13C) of the ipso-C atom (1, 2: 68 Hz; 3: 67 Hz). The complexes [Cd(C6F5)(SR) + H]+, [Cd(SR)2 + H]+, and [Cd2(SR)3]+ were identified in the Cl mass spectra (iso-butane) of 2 and 3.

Download Full-text

Synthesis and characterization of chlorophyll a enol derivatives: Chlorophyll a tert-butyldimethylsilyl-enol ether and 131-deoxo-131, 132-didehydro-chlorophyll a

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424616500486 ◽

2016 ◽

Vol 20 (05) ◽

pp. 590-601

Author(s):

Paavo H. Hynninen ◽

Markku Mesilaakso

Keyword(s):

Chlorophyll A ◽

Mass Spectra ◽

Electronic Absorption Spectra ◽

Enol Ether ◽

Sterically Hindered ◽

Work Up ◽

Derivatives Of ◽

C Nmr

Using the sterically hindered base, 1,8-diazabicyclo[5.4.0]undec-7-ene, for enolization and tert-butyldimethylsilyl-trifluoromethanesulfonate for silylation, chlorophyll (Chl) [Formula: see text] produced after 15 min at 0 [Formula: see text]C in deaerated pyridine solution under argon, after work-up and chromatographic purification on a sucrose column, tert-butyldimethylsilyl-enol ether of Chl [Formula: see text] in a yield of 77%. The 131-deoxo-131,132-didehydro-chlorophyll [Formula: see text], was obtained in a yield of 23% through a reaction sequence, where Chl [Formula: see text] was first reduced with sodium borohydride to 13[Formula: see text]-hydroxy-Chl [Formula: see text], which via demetalation yielded 13[Formula: see text]-hydroxypheophytin [Formula: see text]. In the presence of the sterically hindered base, 1,8-bis(dimethylamino)naphthalene, trifluoroacetylimidazole dehydrated 13[Formula: see text]-hydroxypheophytin [Formula: see text] to 131-deoxo-131,132-didehydro-pheophytin [Formula: see text], which after metalation yielded 131-deoxo-131,132-didehydro-Chl [Formula: see text]. Using 1,8-bis(dimethylamino)naphthalene and trifluoroacetylimidazole, the straight conversion of 13[Formula: see text]-hydroxy-Chl [Formula: see text] to 131-deoxo-131,132-didehydro-Chl [Formula: see text] was found unsuccessful. The major products were characterized by electronic absorption spectra (UV-vis) and practically completely assigned 1H and [Formula: see text]C NMR spectra. Some intermediates of the syntheses were also characterized by ESI-TOF mass spectra. Compared with Chl [Formula: see text], the macrocyclic ring-current in the synthesized Chl [Formula: see text] enol derivatives was found weakened by the expansion of the [Formula: see text]-system to include the isocyclic ring E. Nevertheless, these enol derivatives were still considered to be diamagnetic and aromatic. The possibility of the functional role of the enol derivatives of chlorophyll in photosynthesis is discussed.

Download Full-text

Application of Capillary GC/MS to the Analysis of Wastes from Chemical Plants. II. Identification of Naphthyl[b]thiophenes and Binaphthyls in Gaseous Releases from the Production of 2-Naphthol

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19940119 ◽

1994 ◽

Vol 59 (1) ◽

pp. 119-125 ◽

Cited By ~ 1

Author(s):

Jiří Čermák ◽

Miloslav Sebránek ◽

Jiří Kulhánek

Keyword(s):

Mass Spectra ◽

Retention Data ◽

Chemical Plants ◽

Capillary Gc

Naphthyl[b]thiophenes were identified in gaseous releases from the production of 2-naphthol based on the elucidation of their mass spectra. The identification was verified by comparison with mass spectra and retention data of the authentic compounds which were synthesized for this purpose. Three isomeric binaphthyls were also found in the industrial releases.

Download Full-text

Characterization of Szovitsia callicarpa Volatile Constituents Obtained by Micro- and Hydrodistillation

Natural Product Communications ◽

10.1177/1934578x1000500226 ◽

2010 ◽

Vol 5 (2) ◽

pp. 1934578X1000500 ◽

Cited By ~ 1

Author(s):

Betül Demirci ◽

Nurgün Küçükboyacı ◽

Nezaket Adıgüzel ◽

K. Hüsnü Can Başer ◽

Fatih Demirci

Keyword(s):

Essential Oil ◽

Plant Material ◽

Radical Scavenging Activity ◽

Radical Scavenging ◽

Free Radical Scavenging ◽

Major Constituent ◽

Spectroscopic Techniques ◽

Volatile Constituents ◽

C Nmr

The volatile constituents of Szovitsia callicarpa Fisch. & C. A. Mey. were obtained from the fruits by microdistillation, due to the limited plant material availability. Initial GC-MS analyses of the obtained material showed an unidentified major constituent with a molecular ion peak at M+ 280. After hydrodistillation of the plant material, the resulting essential oil was also analyzed by GC and GC-MS, simultaneously. In total, twenty-two compounds, representing 98.6% of the microdistilled sample, were identified, whereas seventeen components were detected in the hydrodistilled oil, representing 98.5% of the total. The GC-MS analyses showed that the samples contained an unidentified major constituent, which was further purified from the hydrodistilled essential oil by micro-column chromatography. The structure was elucidated as α-kessyl acetate using 1H- and 13C-NMR spectroscopic and mass spectroscopic techniques. Other major constituents in the analytes were determined as longipinene, longicyclene and kessane. In addition, both samples, as well as the major compound α-kessyl acetate, were tested at 1 mg/mL concentration against the pathogen Candida tropicalis and for its free radical scavenging activity against 2,2-diphenyl-1-picrylhydrazyl (DPPH•) by TLC-bioauthographic techniques. Both preliminary assays at the tested concentration showed no activity.

Download Full-text