Analysis of sesquiterpene hydrocarbons in grape berry exocarp (Vitis vinifera L.) using in vivo-labeling and comprehensive two-dimensional gas chromatography–mass spectrometry (GC×GC–MS)

Philipp P. Könen and
Matthias Wüst

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Published 14 Aug 2019

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1. Graphical Abstract
2. Figure 1: Contour plot of a HS-SPME–GC×GC–TOF–MS chromatogram (TIC) demonstrating the separation of volatile ...
  
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3. Figure 2: Sesquiterpene hydrocarbons found in the headspace of Lemberger (Vitis vinifera subsp. vinifera, clo...
  
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4. Figure 3: Detailed part of the two-dimensional contour plot (Figure 1) to demonstrate the result of a successful feed...
  
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5. Scheme 1: First steps towards the formation of sesquiterpenes. The (S)-germacradienyl cation can be formed fr...
  
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6. Scheme 2: Possible biosynthetic pathways of the sesquiterpene hydrocarbons d₈-α-copaene, d₈-β-copaene, d₈-α-c...
  
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7. Scheme 3: Mechanistic rationale for the generation of the sesquiterpene hydrocarbons δ-cadinene (14), α-copae...
  
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8. Figure 4: MS spectra of genuine (d₀) and deuterium-labeled (d₆ and d₈) α-cubebene (left panel) after administ...
  
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9. Scheme 4: Putative formation pathways of the sesquiterpene hydrocarbons α-ylangene (5), β-ylangene (6), β-bou...
  
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10. Figure 5: MS spectra and expected labeling patterns of A: d₀-α-ylangene, B: d₈-α-ylangene after administratio...
  
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11. Figure 6: Expected labeling patterns of deuterium-labeled, aromatic sesquiterpenes after administration of [6...
  
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12. Figure 7: MS spectra and expected labeling patterns of genuine and deuterium-labeled A: calamenene (isomer) a...
  
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13. Figure 8: MS spectra and expected labeling patterns of genuine (d₀) and deuterium-labeled (d₉) β-elemene afte...
  
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14. Scheme 5: Possible biosynthesis of d₉-β-elemene, d₉-(+)-valencene and d₉-α-guaiene via germacrene A. *An inco...
  
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15. Scheme 6: Mechanistic rationale for the generation of the sesquiterpene hydrocarbons γ-elemene and selina-3,7...
  
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16. Figure 9: Mass spectra and associated structural formulas of d₀-γ-elemene and d₉-γ-elemene after administrati...
  
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17. Figure 10: MS spectra and expected labeling patterns of genuine (d₀) and deuterium-labeled (d₉) guaiazulene af...
  
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18. Scheme 7: Possible synthesis of d₉-guaiazulene, d₉-δ-elemene, d₉-guaia-6,9-diene and d₉-δ-selinene via germac...
  
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19. Scheme 8: Possible biosynthesis of d₆-(E)-β-caryophyllene and d₅-α-humulene starting from farnesyl pyrophosph...
  
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20. Figure 11: MS spectra and expected labeling patterns of d₀-(E)-β-caryophyllene and d₆-(E)-β-caryophyllene afte...
  
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Beilstein J. Org. Chem. 2019, 15, 1945–1961, doi:10.3762/bjoc.15.190

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Archangelolide: A sesquiterpene lactone with immunobiological potential from Laserpitium archangelica

Silvie Rimpelová,
Michal Jurášek,
Lucie Peterková,
Jiří Bejček,
Vojtěch Spiwok,
Miloš Majdl,
Michal Jirásko,
Miloš Buděšínský,
Juraj Harmatha,
Eva Kmoníčková,
Pavel Drašar and
Tomáš Ruml

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Published 13 Aug 2019

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1. Graphical Abstract
2. Figure 1: The structure of the sesquiterpene lactones archangelolide (1) and trilobolide (2).
  
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3. Scheme 1: Reagents and conditions: a) MeOH, TEA, 48 h, yield 32%; b) (i) 5-azidopentanoic acid, DCC, DCM, 90 ...
  
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4. Figure 2: Intracellular localization of archangelolide-dansyl (5) in human cells from osteosarcoma (U-2 OS). ...
  
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5. Figure 3: Co-localization of dansylarchangelolide 5 with a marker of endoplasmic reticulum (top row) and with...
  
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6. Figure 4: Cartoon representation of sarco/endoplasmic reticulum Ca²⁺ ATPase binding pocket with A, C) archang...
  
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7. Figure 5: Molecular surface representation of sarco/endoplasmic reticulum Ca²⁺ ATPase binding pocket with A) ...
  
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8. Figure 6: Structural formulae of (i) thapsigargin, (ii) trilobolide (2), and (iii) archangelolide (1). Red pa...
  
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9. Figure 7: Viability of rat peritoneal cells treated with archangelolide (1), dansylarchangelolide 5 and dansy...
  
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10. Figure 8: NO production in primary rat macrophages. The cells were treated with archangelolide (1) and dansyl...
  
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11. Figure 9: Evaluation of cytokine TNF-α secretion in rat peritoneal cells. Stimulation of primary cells was in...
  
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12. Figure 10: Structure of laserolide.
  
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Beilstein J. Org. Chem. 2019, 15, 1933–1944, doi:10.3762/bjoc.15.189

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Morphology-tunable and pH-responsive supramolecular self-assemblies based on AB₂-type host–guest-conjugated amphiphilic molecules for controlled drug delivery

Yang Bai,
Cai-ping Liu,
Di Chen,
Long-hai Zhuo,
Huai-tian Bu and
Wei Tian

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Published 13 Aug 2019

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1. Graphical Abstract
2. Scheme 1: Schematic illustration of the construction of β-CD-BM₂-based supramolecular self-assemblies, their ...
  
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3. Figure 1: Typical TEM images (a–d) and DLS curves (e) of β-CD-BM₂-based supramolecular self-assemblies at pH ...
  
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4. Figure 2: ¹H NMR spectra of β-CD-BM₂-based supramolecular self-assemblies in DMSO-d₆ (a), D₂O (b) and DCl/D₂O...
  
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5. Figure 3: 2D NMR NOESY spectra in D₂O (a) and D₂O/DCl (b), UV–vis spectra (c) and fluorescence spectra (d) of...
  
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6. Figure 4: Cumulative release curves of DOX-loaded β-CD-BM₂ based SSAs at pH 7.4 and 5.0, respectively.
  
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7. Figure 5: (a) Cell viability of PC-3 cells after incubated with β-CD-BM₂ based FSSAs for 48 h. (b) In vitro c...
  
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8. Figure 6: CLSM images of PC-3 cells incubated with the FSSAs and free DOX·HCl at a concentration of 5 μg/mL. ...
  
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Beilstein J. Org. Chem. 2019, 15, 1925–1932, doi:10.3762/bjoc.15.188

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Complexation of chiral amines by resorcin[4]arene sulfonic acids in polar media – circular dichroism and diffusion studies of chirality transfer and solvent dependence

Bartosz Setner and
Agnieszka Szumna

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Published 12 Aug 2019

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1. Graphical Abstract
2. Figure 1: Structures of the compounds used in this study and labelling scheme for NMR spectra.
  
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3. Figure 2: Spectra of complexes [1(LysOMe)₂], [1(ArgOMe)₂], [1(HisOMe)₂]: ¹H NMR (a–g) and ROESY (h–j) in meth...
  
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4. Figure 3: CD (a) and UV (b) spectra of complexes [1(LysOMe)₂], [1(PheOMe)₂], [1(ValOMe)₂], [1(ArgOMe)₂], and [...
  
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5. Figure 4: DOSY spectra of 1 (a), [1(LysOMe)₂] (b), [1(ArgOMe)₂] (c), [1(HisOMe)₂] (d) and [LysOMe + 1(LysOMe)₂...
  
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6. Figure 5: ¹H NMR spectra of 1 (a), LysOMe (b), ¹H NMR and DOSY spectra of [1(LysOMe)₂] (insets show the shape...
  
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7. Figure 6: ¹H NMR spectra of (R)-2 (a); [1((R)-2] (b); [1 + 1((R)-2] (c) (insets show the shape of signals f, ...
  
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8. Figure 7: ¹H NMR and DOSY spectra of (R)-2 (a); [1(R)-2] (b) (inset show the shape signals f, DMSO-d₆, 298K, ...
  
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Beilstein J. Org. Chem. 2019, 15, 1913–1924, doi:10.3762/bjoc.15.187

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Installation of -SO₂F groups onto primary amides

Jing Liu,
Shi-Meng Wang,
Njud S. Alharbi and
Hua-Li Qin

Letter
Published 09 Aug 2019

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1. Graphical Abstract
2. Figure 1: Representative sulfonyl fluoride compounds applied in medicinal chemistry and chemical biology.
  
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3. Scheme 1: Synthesis background of N-fluorosulfonyl amides and fluorosulfates.
  
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4. Scheme 2: Screening of the substrate scope of amides. Reaction conditions: a mixture of amides 1 (1.0 mmol), ...
  
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5. Scheme 3: Amide resonance model and X-ray single crystal structure of 4e (CCDC 1906002).
  
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6. Scheme 4: The proposed reaction mechanism.
  
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Beilstein J. Org. Chem. 2019, 15, 1907–1912, doi:10.3762/bjoc.15.186

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Tautomerism as primary signaling mechanism in metal sensing: the case of amide group

Vera Deneva,
Georgi Dobrikov,
Aurelien Crochet,
Daniela Nedeltcheva,
Katharina M. Fromm and
Liudmil Antonov

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Published 08 Aug 2019

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1. Graphical Abstract
2. Scheme 1: Conceptual idea for tautomeric metal sensing.
  
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3. Scheme 2: 4-(Phenyldiazenyl)naphthalen-1-ol (1) and tautomeric ligands based on it.
  
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4. Figure 1: The most stable tautomeric form of 6 in neutral state (left) and upon complexation with Mg(ClO₄)₂ (...
  
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5. Figure 2: Absorption spectra of compounds 1 (a) and 6 (b) in acetonitrile (—), chloroform (− · −), dichlorome...
  
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6. Figure 3: Left: Theoretically predicted structure of 6K (blue), overlaid with the X-ray structure (red). Righ...
  
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7. Figure 4: Left: Absorption spectra of 6 with stepwise addition of Mg(ClO₄)₂ in acetonitrile (1 – neutral liga...
  
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8. Figure 5: Normalized spectra of the free ligand 6 (c = 5 × 10⁻⁵ M) and its complexes obtained with Ba(ClO₄)₂,...
  
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9. Scheme 3: Synthetic route of 6.
  
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Beilstein J. Org. Chem. 2019, 15, 1898–1906, doi:10.3762/bjoc.15.185

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Inherent atomic mobility changes in carbocation intermediates during the sesterterpene cyclization cascade

Hajime Sato,
Takaaki Mitsuhashi,
Mami Yamazaki,
Ikuro Abe and
Masanobu Uchiyama

Letter
Published 07 Aug 2019

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1. Graphical Abstract
2. Scheme 1: The regio- and stereoselectivity in quiannulatene and sesterfisherol biosynthesis are determined by...
  
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3. Scheme 2: Reaction mechanism of quiannulatene biosynthesis. GFPP: geranylfarnesyl diphosphate, IM: intermedia...
  
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4. Scheme 3: Reaction mechanisms of sesterfisherol biosynthesis. Sesterfisherol is formed by the hydration of IM...
  
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5. Figure 1: Energy diagram and heat map analysis of 5/12/5 tricycle formation (A) IM1–IM4 in quiannulatene bios...
  
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6. Figure 2: Energy diagram and heat map analysis of conformational change and hydrogen shift (A) IM4–IM6e in qu...
  
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7. Figure 3: Energy diagram and heat map analysis of ring rearrangement (A) IM6e–IM11 in quiannulatene biosynthe...
  
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Beilstein J. Org. Chem. 2019, 15, 1890–1897, doi:10.3762/bjoc.15.184

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Identification of optimal fluorescent probes for G-quadruplex nucleic acids through systematic exploration of mono- and distyryl dye libraries

Xiao Xie,
Michela Zuffo,
Marie-Paule Teulade-Fichou and
Anton Granzhan

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Published 06 Aug 2019

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1. Graphical Abstract
2. Figure 1: Some di- and mono-styryl dyes previously reported as fluorescent “light-up” probes for G4-DNA and R...
  
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3. Figure 2: Design of a library of di- and mono-styryl dyes. Counter-ions are omitted for the sake of clarity.
  
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4. Scheme 1: A, B) General synthesis of A) distyryl and B) mono-styryl dyes via Knoevenagel condensation route. ...
  
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5. Scheme 2: Synthesis of I3–5 and I15.
  
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6. Figure 3: Representative absorption spectra of distyryl dyes: A) 1d, B) 1ð, C) 1f, D) 1u, E) 10a and F) 12a i...
  
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7. Figure 4: Representative absorption spectra of the distyryl dyes (c = 10 µM in MeOH) demonstrating the influe...
  
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8. Figure 5: Heat map of the relative emission intensity enhancement (I/I₀) of styryl dyes and thioflavin T (ThT...
  
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9. Figure 6: Analysis of the light-up response matrix of the dyes. The average light-up factor of each dye with ...
  
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10. Figure 7: PC1 vs PC2 plot obtained from the principal component analysis of the light-up data matrix for all ...
  
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11. Figure 8: Dual-dye conformational analysis of an extended panel of 33 DNA oligonucleotides. This is performed...
  
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12. Figure 9: Selected probes featuring high fluorimetric response towards G4 structures.
  
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13. Figure 10: Photographs of solutions of A) distyryl dyes 1p and 1u; B) mono-styryl dyes 17a and 18a, in the abs...
  
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Beilstein J. Org. Chem. 2019, 15, 1872–1889, doi:10.3762/bjoc.15.183

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A metal-free approach for the synthesis of amides/esters with pyridinium salts of phenacyl bromides via oxidative C–C bond cleavage

Kesari Lakshmi Manasa,
Yellaiah Tangella,
Namballa Hari Krishna and
Mallika Alvala

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Published 05 Aug 2019

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1. Graphical Abstract
2. Scheme 1: Comparison of our work with previous studies.
  
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3. Scheme 2: Scope of pyridinium salts and benzylamine substrates. Reaction conditions: 1 (1 mmol), 2 (1 mmol), ...
  
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4. Scheme 3: Scope of pyridinium salts and benzyl alcohol substrates. Reaction conditions: 1 (1 mmol), 4 (1 mmol...
  
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5. Scheme 4: Scope of pyridinium salts, primary and secondary amine substrates. Reaction conditions: 1 (1 mmol), ...
  
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6. Scheme 5: Control experiments for the oxidative cleavage of C–C bonds.
  
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7. Scheme 6: Plausible reaction mechanism for the synthesis of N-alkylated benzamides 3.
  
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Beilstein J. Org. Chem. 2019, 15, 1864–1871, doi:10.3762/bjoc.15.182

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Halide metathesis in overdrive: mechanochemical synthesis of a heterometallic group 1 allyl complex

Ross F. Koby,
Nicholas R. Rightmire,
Nathan D. Schley,
Timothy P. Hanusa and
William W. Brennessel

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Published 02 Aug 2019

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1. Graphical Abstract
2. Figure 1: Portion of the polymeric chain of [CsKA'₂], with thermal ellipsoids drawn at the 50% level. Hydroge...
  
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3. Figure 2: Partial packing diagram of [CsKA'₂], illustrating some of the interchain contacts, predominantly K1^…...
  
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4. Figure 3: Portion of the polymeric chain of [(C₆H₆)KA']_∞, with thermal ellipsoids drawn at the 50% level. Hyd...
  
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Beilstein J. Org. Chem. 2019, 15, 1856–1863, doi:10.3762/bjoc.15.181

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