A purge and trap technique to capture volatile compounds combined with comprehensive two‐dimensional gas chromatography/time‐of‐flight mass spectrometry to investigate the effect of sulfur‐fumigation on Radix Angelicae Dahuricae

Sulfur‐fumigation is known to reduce volatile compounds that are the main active components in herbs used in herbal medicine. We investigated changes in chemical composition between sun‐dried and sulfur‐fumigated Radix Angelicae Dahuricae using a purge and trap technique to capture volatile compounds, and two‐dimensional gas chromatography/time‐of‐flight mass spectrometry for identification. Using sun‐dried Radix Angelicae Dahuricae samples as a reference, the results showed that 73 volatile compounds, including 12 sulfide compounds, were found to be present only in sulfur‐fumigated samples. Furthermore, 32 volatile compounds that were found in sun‐dried Radix Angelicae Dahuricae samples disappeared after sulfur‐fumigation. The proposed method can be applied to accurately discriminate sulfur‐fumigated Radix Angelicae Dahuricae from different commercial sources. Copyright © 2014 John Wiley & Sons, Ltd.     

Thickness dependence of thermally induced changes in surface and bulk properties of Nafion® nanofilms

Thermally induced changes in surface wettability, dewetting behavior, and proton transport of “self‐assembled” nanothin Nafion^® films (4–300 nm) on SiO₂ substrate is reported. Thermal annealing induces switching of the surface wettability of 55 nm and thinner films from hydrophilic to super‐hydrophobic. Thickness dependence of this behavior is observed with higher annealing temperature required for lower thickness films, indicating highly restrictive mobility of Nafion^® ionomer as film thickness decreases. Dewetting is only observed for 4‐nm thin film. Significant suppression in proton conductivity upon thermal annealing was noted. Similarly, two other bulk properties, water uptake and swelling, were found to decrease upon annealing. This work reports a systematic examination of the thickness dependence of thermally induced changes in both surface and bulk properties of ultra‐thin Nafion^®. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1267–1277     

Enantioselective comprehensive two‐dimensional gas chromatography. A route to elucidate the authenticity and origin of Rosa damascena Miller essential oils

The analysis of Bulgarian and Turkish Rosa damascena Miller essential oils was performed by flow‐modulated comprehensive two‐dimensional gas chromatography using simultaneous detection of the second column effluent by flame ionization and quadrupole mass spectrometric detection. Enantioselective separations were obtained by running the samples on 2,3‐di‐O‐ethyl‐6‐O‐tert‐butyldimethylsilyl‐β‐cyclodextrin column as the first column and on polyethylene glycol as the second column. The determination of enantiomeric or diastereomeric excess of some terpenoic solutes is a possible route for quality or authenticity control as well as for the elucidation of the country of origin.     

Efficient extraction of proteins from recalcitrant plant tissue for subsequent analysis by two‐dimensional gel electrophoresis

Protein extraction for two‐dimensional electrophoresis from tissues of recalcitrant species is quite problematic and challenging due to the low protein content and high abundance of contaminants. Proteomics in Shorea robusta is scarcely conducted due to the lack of a suitable protein preparation procedure. To establish an effective protein extraction protocol suitable for two‐dimensional electrophoresis in Shorea robusta, four procedures (borate buffer/trichloroacetic acid extraction, organic solvent/trichloroacetic acid precipitation, sucrose/Tris/phenol, and organic solvent/phenol/sodium dodecyl sulfate) were evaluated. Following these, proteins were isolated from mature leaves and were analyzed for proteomics, and also for potential contaminants, widely reported to hinder proteomics. The borate buffer/trichloroacetic acid extraction had the lowest protein yield and did not result in any banding even in one‐dimensional electrophoresis. In contrast, organic solvent/phenol/sodium dodecyl sulfate extraction allowed the highest protein yield. Moreover, during proteomics, organic solvent/phenol/sodium dodecyl sulfate extracted protein resolved the maximum number (144) of spots. Further, when proteins were evaluated for contaminants, significant (77–95%) reductions in the nucleic acids, phenol, and sugars were discernible with refinement in extraction procedure. Accumulated data suggested that the organic solvent/phenol/sodium dodecyl sulfate extraction was the most effective protocol for protein isolation for proteomics of Shorea robusta and can be used for plants that have a similar set of contaminants.     

One‐dimensional CuII coordination polymers containing C2h‐symmetric 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate linkers

Two new one‐dimensional Cu^II coordination polymers (CPs) containing the C_2h‐symmetric terphenyl‐based dicarboxylate linker 1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylate (3,3′‐TPDC), namely catena‐poly[[bis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ⁴O,O′:O′′:O′′′] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂]·H₂O}_n, (I), and catena‐poly[[aquabis(dimethylamine‐κN)copper(II)]‐μ‐1,1′:4′,1′′‐terphenyl‐3,3′‐dicarboxylato‐κ²O³:O^3′] monohydrate], {[Cu(C₂₀H₁₂O₄)(C₂H₇N)₂(H₂O)]·H₂O}_n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4‐diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours, i.e. violet plates for (I) and blue needles for (II), both of which were analysed by X‐ray crystallography. The 3,3′‐TPDC bridging ligands coordinate the Cu^II ions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one‐dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutually trans positions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one‐dimensional coordination polymer chains, forming a two‐dimensional network in (I) and a three‐dimensional network in (II).     

A two‐dimensional cadmium(II) coordination polymer based on 1‐cyanomethyl‐4‐aza‐1‐azoniabicyclo[2.2.2]octane and thiocyanate ligands

A cadmium–thiocyanate complex, poly[(1‐cyanomethyl‐4‐aza‐1‐azoniabicyclo[2.2.2]octane‐κ⁴N)octakis‐μ₂‐thiocyanato‐κ⁸N:S;κ⁸S:N‐tricadmium(II)], [Cd₃(C₈H₁₄N₃)₂(NCS)₈]_n, was synthesized by the reaction of 1‐cyanomethyl‐4‐aza‐1‐azoniabicyclo[2.2.2]octane chloride, cadmium nitrate tetrahydrate and potassium thiocyanide in aqueous solution. In the crystal structure, there are two independent types of Cd^II cation (one on a centre of inversion and one in a general position) and both are in distorted octahedral coordination environments, coordinated by N and S atoms from different ligands. Neighbouring Cd^II cations are linked together by thiocyanate bridges to form a two‐dimensional network. Hydrogen‐bonding interactions are involved in the formation of a three‐dimensional supramolecular network.     

Hirshfeld surface analysis of two new phosphorothioic triamide structures

Hirshfeld surfaces and two‐dimensional fingerprint plots are used to analyse the intermolecular interactions in two new phosphorothioic triamide structures, namely N,N′,N′′‐tris(3,4‐dimethylphenyl)phosphorothioic triamide acetonitrile hemisolvate, P(S)[NHC₆H₃‐3,4‐(CH₃)₂]₃·0.5CH₃CN or C₂₄H₃₀N₃PS·0.5CH₃CN, (I), and N,N′,N′′‐tris(4‐methylphenyl)phosphorothioic triamide–3‐methylpiperidinium chloride (1/1), P(S)[NHC₆H₄(4‐CH₃)]₃·[3‐CH₃‐C₅H₉NH₂]⁺·Cl⁻ or C₂₁H₂₄N₃PS·C₆H₁₄N⁺·Cl⁻, (II). The asymmetric unit of (I) consists of two independent phosphorothioic triamide molecules and one acetonitrile solvent molecule, whereas for (II), the asymmetric unit is composed of three components (molecule, cation and anion). In the structure of (I), the different components are organized into a six‐molecule aggregate through N—H...S and N—H...N hydrogen bonds. The components of (II) are aggregated into a two‐dimensional array through N—H...S and N—H...Cl hydrogen bonds. Moreover, interesting features of packing arise in this structure due to the presence of a double hydrogen‐bond acceptor (the S atom of the phosphorothioic triamide molecule) and of a double hydrogen‐bond donor (the N—H unit of the cation). For both (I) and (II), the full fingerprint plot of each component is asymmetric as a consequence of the presence of three fragments. These analyses reveal that H...H interactions [67.7 and 64.3% for the two symmetry‐independent phosphorothioic triamide molecules of (I), 30.7% for the acetonitrile solvent of (I), 63.8% in the phosphorothioic triamide molecule of (II) and 62.9% in the 3‐methylpiperidinium cation of (II)] outnumber the other contacts for all the components in both structures, except for the chloride anion of (II), which only receives the Cl...H contact. The phosphorothioic triamide molecules of both structures include unsaturated C atoms, thus presenting C...H/H...C interactions: 17.6 and 21% for the two symmetry‐independent phosphorothioic triamide molecules in (I), and 22.7% for the phosphorothioic triamide molecule of (II). Furthermore, the N—H...S hydrogen bonds in both (I) and (II), and the N—H...Cl hydrogen bonds in (II), are the most prominent interactions, appearing as large red spots on the Hirshfeld surface maps. The N...H/H...N contacts in structure (I) are considerable, whereas for (II), they give a negligible contribution to the total interactions in the system.     

Halogen‐bonded adduct of 1,2‐dibromo‐1,1,2,2‐tetrafluoroethane and 1,4‐diazabicyclo[2.2.2]octane

Halogen bonding is an intermolecular interaction capable of being used to direct extended structures. Typical halogen‐bonding systems involve a noncovalent interaction between a Lewis base, such as an amine, as an acceptor and a halogen atom of a halofluorocarbon as a donor. Vapour‐phase diffusion of 1,4‐diazabicyclo[2.2.2]octane (DABCO) with 1,2‐dibromotetrafluoroethane results in crystals of the 1:1 adduct, C₂Br₂F₄·C₆H₁₂N₂, which crystallizes as an infinite one‐dimensional polymeric structure linked by intermolecular N...Br halogen bonds [2.829 (3) Å], which are 0.57 Å shorter than the sum of the van der Waals radii.     

A two‐dimensional layered CdII coordination polymer with a three‐dimensional supramolecular architecture incorporating mixed multidentate N‐ and O‐donor ligands

The combination of N‐heterocyclic and multicarboxylate ligands is a good choice for the construction of metal–organic frameworks. In the title coordination polymer, poly[bis{μ₂‐1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole‐κ²N³:N⁴}(μ₄‐butanedioato‐κ⁴O¹:O^1′:O⁴:O^4′)(μ₂‐butanedioato‐κ²O¹:O⁴)dicadmium], [Cd(C₄H₄O₄)(C₉H₈N₆)]_n, each Cd^II ion exhibits an irregular octahedral CdO₄N₂ coordination geometry and is coordinated by four O atoms from three carboxylate groups of three succinate (butanedioate) ligands and two N atoms from two 1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole (bimt) ligands. Cd^II ions are connected by two kinds of crystallographically independent succinate ligands to generate a two‐dimensional layered structure with bimt ligands located on each side of the layer. Adjacent layers are further connected by hydrogen bonding, leading to a three‐dimensional supramolecular architecture in the solid state. Thermogravimetric analysis of the title polymer shows that it is stable up to 529 K and then loses weight from 529 to 918 K, corresponding to the decomposition of the bimt ligands and succinate groups. The polymer exhibits a strong fluorescence emission in the solid state at room temperature.