Comprehensive chemical derivatization for gas chromatography-mass spectrometry-based multi-targeted profiling of the major phytohormones

In the present investigation we report selection of the N-methyl-N-(tert.-butydimethylsilyl)trifluoroacetamide (MTBSTFA) reagent as the most comprehensive derivatization protocol among 17 tested reactions covering trifluoroacetylation, pentafluorobenzylation, methylations, and trimethylsilylations. MTBSTFA allowed easy and robust tert.-butyldimethylsilyl derivatization of 1-aminocyclopropane-1-carboxylic acid, indole-3-acetic acid, (+/-)-jasmonic acid, salicylic acid, (+/-)-abscisic acid, meta-topolin, and trans-zeatin. Detection limits as analysed by selected ion monitoring quadrupole GC-MS were 0.2, 0.01, 1.0, 0.02, 0.3, 0.3, and 0.9 pmol of injected substance, respectively. Analysis of gibberellic acid A3, trans-zeatin riboside and (+/-)-abscisic acid-beta-D-glucopyranosyl ester was best when coupled by splitting extracts and trimethysilylation. The MTBSTFA derivatization protocol was optimised, and validated. The preparation was insensitive to 2% residual water and to < or = 1 day storage at room temperature. The final scheme was highly reproducible and successfully applied to extracts from approximately 300 mg (fresh mass) of tobacco (Nicotiana tabacum) root and Arabidopsis thaliana seedling.     

A concise synthesis of ortho-substituted aryl-acrylamides—potent activators of soluble guanylyl cyclase

Horner-Emmons reaction of phosphonate amides with aldehydes leads to generation of o-substituted aryl-acrylamides. These compounds have been shown to be useful to quickly establish structure-activity relationships (SAR) for soluble guanylyl cyclase (sGC) activator drug discovery.     

Resonant crossover of terahertz loss to the gain of a Bloch oscillating InAs/AlSb superlattice

Terahertz absorption in waveguides loaded with InAs/AlSb super-superlattice mesas reveals a frequency dependent crossover from loss to gain that is related to the Stark ladder produced by an applied dc electric field. Electric field domains appear to be suppressed in the super-superlattice composed of many very short segments of superlattice, interrupted by heavily doped InAs regions. Resonant crossover is indicated by an increase in terahertz transmission as the Stark splitting or Bloch frequency determined by the applied dc electric field exceeds the measurement frequency.     

Quantitative determination of hydroxylamine

This paper is a survey of 66 studies from the literature and presents a review of the quantitative methods most widely used for the determination of hydroxylamine and its salts. Volumetric, electrochemical and spectrophotometric methods are discussed, compared and evaluated.     

O-protected derivatives of N-hydroxyamino acids

Various N-alkoxyamino acids were studied, and N-benzyloxyamino acids were chosen as the most suitable substrates for unambiguous synthesis of N-hydroxy peptides.     

Synthesis of 4,5-diaryl-1H-pyrazole-3-ol derivatives as potential COX-2 inhibitors

4,5-Diaryl-1H-pyrazole-3-ol was utilized as a versatile template to synthesize several classes of compounds such as pyrazolo-oxazines 7, pyrazolo-benzooxazines 9, pyrazolo-oxazoles 10, and its analogues 11a-c as potential COX-2 inhibitors. Compounds 11b,c were successfully synthesized with use of pyridinium p-toluenesulfonate mediated cyclization of the ketal intermediate. Diaryl-pyrazolo-benzooxazepine analogues were synthesized by using Cu-mediated cyclization of the O-alkylated arylbromide intermediate. Arylsulfonamides were synthesized efficiently on a large scale with 4-[4-(4-fluorophenyl)-5-hydroxy-2H-pyrazol-3-yl]benzenesulfonamide 31 template readily synthesized from commercially available 4-sulfamoyl benzoic acid 29. The structure of a representative compound from each class was confirmed by X-ray crystallography. Selected compounds tested for inhibitory activity against COX-1 and COX-2 enzymes showed good selectivity for COX-2 versus COX-1 enzyme.     

An efficient one-pot synthesis of substituted 2-arylbenzo[b]thiophene derivatives

This communication describes an efficient one-pot procedure for the synthesis of 2-arylbenzo[b]thiophene derivatives via reaction of o-halo or nitro aryl carbonyl compounds with benzyl mercaptans in the presence of an excess of anhydrous K₂CO₃ at elevated temperature.     

X-ray analysis and spectral data of β-[N-phenyl,N-(β′-bromo-cinnamoyl)-amino]-cinnamanilide reveal the course of reaction of benzoylacetanilide with POBr3

The reaction of benzoylacetanilide with the excess of POBr₃ furnished monomolecular products and the bimolecular-[N-phenyl,N-(-bromo-cinnamoyl)-amino]-cinnamanilide. Its structure was elucidated by means of elemental analysis, IR,¹H NMR and mass spectral data as well as X-ray analysis, which proved that the reaction mentioned goes via condensation. C₃₀H₂₃BrN₂O₂ crystallizes with two independent molecules in an asymmetric unit in the orthorhombic space groupP2₁2₁2₁ witha ₃=9.834(3),b=19.614(2),c=26.450(6) Å,Z=8,V=5101(4) ų,D _m =1.34,D _x =1.36 mg m^–3,F(000)=2151,M _r =523.107,=2.25 mm^–1, (CuK)=1.54178 Å,T=293 K; the finalR factor was 0.067.