Identification of calcium carbide-ripened sapota (Achras sapota) fruit by headspace SPME-GC-MS.

The effect of post-harvest ripening by ethylene and calcium carbide was studied by headspace solid-phase microextraction gas chromatography mass spectrometry (HS-SPME-GC-MS) method. Sapota (sapodilla) fruits were ripened with ethylene gas, technical grade calcium carbide and pure calcium carbide ripeners and the samples were homogenised after complete ripening. The samples were subjected to HS-SPME-GC-MS and the obtained results showed the presence of various alcohols, aldehydes, acids, ketones and esters which were commonly present in the samples. The fruit samples ripened with technical grade calcium carbide showed the presence of 3,5-dimethyl-1,2,4-trithiolane isomers, which can be used as markers to identify sapota fruits ripened with technical grade calcium carbide. The technical grade calcium carbide contains divinyl sulphide which might have been transformed into the trithiolane isomers. These isomers were not observed in the fruits ripened with pure calcium carbide and also with ethylene gas. Hence the formation of trithiolane residues may be attributed to the presence of divinyl sulphide impurity present in calcium carbide and its conversion due to the action of ethylene releasing enzymes present in the fruits.

Determination of 2-chloroethylphosphonic acid and its intermediate vinylphosphonic acid from artificially ripened sapota fruit by modified dispersive solid-phase extraction cleanup and gas chromatography/mass spectrometry analysis.

RATIONALE: Fruit is generally ripened after harvesting using artificial ripeners such as ethylene, calcium carbide, and ethephon (2-chloroethylphosphonic acid), which can release some residues into the fruits. These residues must be within the maximum levels described in various international standards. The presence of the residues of artificial ripeners must be verified using sensitive and selective detection methods. METHODS: The residues of ethephon and vinylphosphonic acid (VPA) were extracted from the pulp of sapota fruit using acetone, and the extract was treated with MgSO4 to remove residual water. The extract was subjected to dispersive solid-phase extraction cleanup using DSC-6S sorbent and graphitized carbon black mix, and the cleaned sample was evaporated to dryness and reconstituted in ether containing diazomethane. The analytes were quantitatively identified using gas chromatography/mass spectrometry. RESULTS: The developed method was observed to be linear in the concentration range of 1-5000 ng/g, and the limits of detection and quantification of the method were 1 and 2 ng/g, respectively, for both ethephon and VPA residues. The inter-day and intra-day precision was below 15%. The developed method was used for the quantification of ethephon residues from sapota fruit ripened with 100, 200, 500, 1000, 5000, and 10 000 mg/L solutions of ethephon, and ethephon residues were detected in the pulp samples up to a concentration of 5 ng/g. VPA residues were not detected in the fruit pulp; however, the washing solution of fruit ripened with a 10 000 mg/L ethephon solution showed VPA residues. CONCLUSIONS: The validated method exhibited high sensitivity for the analytes with a limit of quantification of 2 ng/g, which is lower than the described maximum residue level of 0-5 µg/g. The ethephon residues were below the maximum residue limits in the pulp of sapota fruit ripened with ethephon solutions up to 10 000 mg/L concentration.

Synthesis of 8',11'-dihydrospiro[cyclohexane-1,2'-oxepino[2,3-h] chromen]-4'(3'H)-ones with ring closing metathesis as a key step.

A series of novel hybrid molecular entities incorporating various spiro chromanone scaffolds onto the benzannulated oxepine core moiety were synthesised using allylation, Claisen rearrangement, Kabbe condensation and Ring Closing Metathesis (RCM) as a key step. During the synthesis we found that the nitrogen functionality in the substrate influences significantly the catalyst load due to electronic effects. Several iterations have been carried out to achieve complete conversion to products 6a-6e.