A novel on-tissue cycloaddition reagent for mass spectrometry imaging of lipid C=C position isomers in biological tissues

Application of matrix-assisted laser desorption/ionization mass spectrometry imaging(MALDI-MSI) to investigate the spatiotemporal alterations of lipids in biological tissues has brought many significant results.However, the presence of structural isomers varying in C=C double bond(DB) locations makes isomerresolved MSI an urgent need. Herein, we introduce a new type of light-driven on-tissue [2 + 2] cycloaddition reaction coupled with MALDI-MS/MS imaging to identify lipid DB position isomers and their spatial signatures in biological tissues. 3-Benzoylpyridine was introduced as a novel derivatization reagent, and it exhibited great reactivity toward lipid C=C bond to form oxetanes under both ultraviolet light and visible light irradiation. With this approach, DB position isomers of lipids were imaged with highly differential levels in distinct regions of rat brain, providing an accurate and spatially resolved approach to study tissue lipidomics.

Differentiation of Positional Isomers of Propyl Alcohols Using Filament-Induced Fluorescence

We experimentally demonstrate the recognition of positional isomers of propyl alcohol vapor through nonlinear fluorescence induced by high-intensity femtosecond laser filaments in air. By measuring characteristic fluorescence of n-propyl and isopropyl alcohol vapors produced by femtosecond filament excitation, it is found that they show identical spectra, that is, those from molecular bands of CH, C2, Nit, OH and CN, while the relative intensities are different. By comparing the ratios of the CH and C2 signals, the two propyl alcohol isomers are differentiated. The different signal intensities are ascribed to different ionization potentials of the two isomer molecules, leading to different production efficiencies of fluorescing fragments.

Effective assignment of positional isomers in dimeric shikonin and its analogs by ^(1)H NMR spectroscopy

An approach for distinguishing two types of positional isomers of dimeric shikonin and its analogs was explored with ^(4)JC,H long-range correlation by prolonging the acquisition time at ^(2,3)JC,H values of 2.0 and 8.0Hz.Furthermore,the ^(1)H(proton)nuclear magnetic resonance(NMR)pattern of phenolic hydroxyl protons was developed as a“diagnosis signal”to ascertain the relative location of each side chain in DMSO-d_(6) at sample concentrations of 0.022-0.034 mol/L.The chemical shift differences of 0.6ppm between OH-5' and OH-1 and between OH-8'and OH-4 are assigned to Type A and Type B,respectively.All reported ambiguous structures were corrected by this pattern.Additionally,the steric structures of isolated compounds were elucidated by quantum chemical calculations of electronic circular dichroism(ECD)spectra.

Positional Isomeric Thiophene-Based π-Conjugated Chromophores:Synthesis,Structure,and Optical Properties

A series of positional isomeric chromophores o-TC,m-TC,and p-TC,in which electron-rich thiophene moieties were connected byπ-conjugated bridges,were divergently synthesized and characterized.Single-crystal X-ray diffraction analysis revealed an intriguing zipper-like packing mode which was adopted by m-TC in the solid state.Subsequently,UV−vis absorption spectra and fluorescence spectra in a series of solvents were investigated.The nearly coplanar para isomer p-TC was found to have the most intense UV−vis absorption,fluorescence emission,and the highest photoluminescence quantum yield.The molecule structure,electronic nature,and origination of the absorption of p-TC were revealed through density functional theory calculations.Interestingly,all three positional isomers exhibited strong and stable electrochemiluminescence emission,which enriched the existing knowledge on the optical properties of thiophene-based oligomers.

Selectivity of New β-Cyclodextrin Derivatives as CGC Stationary Phases and Application for the Analysis of Volatile Compounds in Traditional Chinese Medicines

New cyclodextrin derivatives （CDs）, heptakis（2, 6-di- O-methyl-3- O-methoxymethyl）-β-CD （ Ⅰ ） and heptakis（2, 3, 6-tri-O-methoxymethyl）-β-CD （ Ⅱ ）, were investigated for their chromatographic performance as stationary phases for capillary gas chromatography （CGC）. Both of the CDs exhibited good selectivity and satisfactory separation for test mixtures and aromatic positional isomers, and volatile compounds from Ligusticurn chuanxiong Hort. Additionally, the selectivity and elution orders of major compounds were compared with a well-recognized commercial column on the basis of the results by gas chromatography-mass spectrometry （GC-MS）. The present work demonstrates the good selectivity of the two new CDs and can be used as GC stationary phases for the separation of positional isomers and analytes in complex samples.

Mass spectrometric identification of double bond positional isomers of hexadecenyl acetate without chemical derivatization

A method for the identification of the double bond positional isomers of hexadecenyl acetate has been established by analysing similarity of the mass spectra patterns on a fuzzy classification, in which the intensity ratios of six diagnostic pairs of the predominant ions were selected as standard parameters for the characterization of the double bond position. The procedure was tested with △2 to △15-isomers of chemically unmodified hexadecenyl acetate, and the original double bond position in the acetates was located unambiguously.

Analysis of the linkage positions and isomers of monosaccharide units in oligosaccharides by negative secondary ion mass spectrometry in combination with the stereoselective reaction with substituted boronic acid

The negative secondary ion mass spectrometry,in combination with the stereoselective derivatizations with substituted boronic acid RB(OH)_2,was used in the analysis of fourteen oligosac- charides.The mass spectra of the derivatives provide information on their linkage Positions and iso- merism of the individual monoscaccharide units.The results indicated that among the derivatives of the oligosaccharides analyzed,those with 1—4 and 1—6 linkages all presented the ion peaks at m/z 287,sometimes one more peak at m/z 449.Furthermore,a relationship was found between the linkage positions and the intensity orders of the derivative ions.Finally,the derivatives of the disaccharides with a galactose presented an intense ion peak at m/z 347,and those of oligosaccharides with 1—6 linkage to a galactose at terminal presented the ion at m/z 317.In the case of oligosaccharides with a fructose residue,characteristic ion of m/z 155 was produced.The conditions of stereoselective derivatizations and mass spectrometry were studied,in order to obtain a better reproducibility of the mass spectra.

A novel formula for location of double bond in alkenyl acetates and alcohols based on mass spectral data of dimethyl disulfide derivatives

A new formula was presented for locating double bond position in dodecenols, tetradcenols hexadecenols and their acetates, based on mass spectral data of dimethyl disulfide derivatives. In this procedure, molecular ion and base peak ion were utilized as characteristic parameters to identify the positional isomers. The method was tested with mass spectra of 25 dimethyl disulfide derivatives of mono-unsaturated acetates and alcohols, and the original double-bond position in each isomer was located unambiguously.