Isomer Distribution Research Articles

Understanding Selectivity in Product Distributions from Laser Ablation of Organic Liquids.

Pulsed laser ablation in organic solvents is widely used to produce oxide-free metal and metal carbide nanoparticles, often with carbon coatings resulting from laser-induced reactions in the organic solvent. To gain insight into how the molecular structure of the solvent affects these reaction pathways, this work investigates ablation of the C6H14 isomers n-hexane, 2-methylpentane, and 3-methylpentane through characterization of the gas and liquid products with mass spectrometry. Ablation of each C6H14 isomer produces a distinct distribution of product molecular weights and isomers. 2-methylpentane preferentially produces C3 and C9, whereas 3-methylpentane produces C2, C4, C8, and C10 products. These preferential product distributions, along with the lack of such selectivity in n-hexane, arise from differences in the most favorable C-C bond scission pathways in each C6H14 isomer. Moreover, the particular isomers of C8H18, C9H20, C10H22, and C12H26 produced by ablation of each C6H14 isomer indicate that the vast majority of reaction pathways involve addition reactions between a fragment radical and parent C6H14 or between two C6H14 molecules, without molecular rearrangement. This propensity toward direct addition suggests that the chemical reactions induced by ultrashort pulsed laser ablation proceed on faster time scales than those of radical rearrangements.

Heterogeneous toluene nitration with mixed acid in microreactors: Reaction regime, characteristics and kinetic models

It is critical for reactor design and process safety to determine the reaction kinetics for toluene nitration. Herein, a continuous-flow platform based on capillary microreactors was established. First, reaction regimes for toluene nitration and its consecutive side reaction (MNT (mononitrotoluene) nitration) were identified. On this basis, the influence of process parameters on conversion of toluene, selectivity of MNT and DNT (dinitrotoluene) and their isomer distribution were meticulously examined, including molar ratio of reactants, sulfuric acid strength, reaction temperature, and residence time. Subsequently, reaction kinetic models coupled with mass transfer were developed, allowing the simultaneous kinetic determination for toluene nitration and MNT nitration. It was found that the logarithm of the observed kinetic constant is proportional to the sulfuric acid strength. The kinetic parameters under 72.7 to 80.1 wt% sulfuric acid strengths were obtained. The outcomes provide a basis for process intensification and optimization of toluene nitration as well as other similar aromatics.

Mass Spectrometry Imaging for the Characterization of C═C Localization in Unsaturated Lipid Isomers at the Single-Cell Level.

Unsaturated lipids with carbon-carbon double bonds (C═C) have been implicated in the pathogenesis of various diseases. While mass spectrometry imaging (MSI) has been employed to map the distribution of lipid isomers in tissue sections, the identification of lipid C═C positional isomers at the single-cell level using MSI poses a significant challenge. In this study, we developed a novel approach utilizing ToF-SIMS in conjunction with the Paternò-Büchi (P-B) photochemical reaction to characterize the C═C localization in unsaturated lipid isomers at the single-cell level. The P-B reaction was employed to produce adduct products, which were subsequently subjected to collision-induced dissociation by the primary ion beam of ToF-SIMS to generate characteristic ion pairs indicative of the presence of C═C bonds. Utilizing this approach, lipid isomers in brain and skeletal tissues from mice, as well as different cell lines, were visualized at single-cell resolution. Furthermore, distinct variations in the composition of FA 18:1 isomers across different microregions and cell types were revealed. Our P-B ToF-SIMS approach enables the accurate identification and characterization of complex lipid structures with remarkable spatial resolution and can be helpful in understanding the physiological role of these C═C positional isomers.

External surface Al-rich ZSM-48 zeolite with high efficient n-dodecane hydroisomerization activity

ZSM-48 zeolites with exterior Al-rich (Z-48-Sx) are synthesized by the recrystallization method. The crystal structure of Z-48-Sx with the Al-rich outer layer is verified by analyzing the crystallization process of Z-48-Sx and the EDS of the ultrathin section. The diffusion properties of Z-48-S3 and Z-48-C are investigated by the zero-length column (ZLC) method, and the synthesized ZSM-48 zeolite with an Al-rich external layer effectively improves the diffusion ability. The effective diffusion constants of Z-48-S3 are 53 %–102 % higher than those of the conventional ZSM-48 (Z-48-C). Meanwhile, the values of turnover frequency (TOF) of Z-48-S3 are increased by 14 %–63 % at similar n-dodecane conversions compared with Z-48-C, which is closely related to the diffusion characteristics. In addition, the depth of hydroisomerization (Iiso) of Z-48-S3 is decreased by 65.3 %, and the isomerization selectivity is increased by 52.5 % at 340 °C compared with that of Z-48-C. Hence, the ZSM-48 molecular sieves synthesized by the recrystallization hydrothermal method are beneficial for controlling the depth of hydroisomerization of the catalyst and reducing the occurrence of the cracking reaction. Meanwhile, the isomer distribution does not change significantly compared with that of the conventional ZSM-48, and the 5-methylundecane is still the main isomerization product.

The isomer distribution of C6H6 products from the propargyl radical gas-phase recombination investigated by threshold-photoelectron spectroscopy

The resonance-stabilization of the propargyl radical (C3H3) makes it among the most important reactive intermediates in extreme environments and grants it a long enough lifetime to recombine in both terrestrial combustion media and cold molecular clouds in space. This makes the propargyl self-reaction a pivotal step in the formation of benzene, the first aromatic ring, to eventually lead to polycyclic aromatic hydrocarbons in a variety of environments. In this work, by producing propargyl radicals in a flow tube where propyne reacted with F atoms and probing the reaction products by mass-selected threshold-photoelectron spectroscopy (TPES), we identified eight C6H6 products in total, including benzene. On top of providing the first comprehensive measurements of the branching ratios of the eight identified C6H6 isomers in the propargyl self reaction products (4 mbar, 298 K conditions), this study also highlights the advantages and disadvantages of using isomer-selective TPES to identify and quantify reaction products.

Temperature and nutrients control the presence and distribution of long-chain diols in Swiss lakes

Long-chain diols are biomarkers commonly used in the marine realm to reconstruct several environmental parameters such as sea surface temperature and salinity. However, they are also produced in lacustrine and slow-flowing river environments, a characteristic that has proved to be useful to trace past riverine inputs in coastal sedimentary records. So far, their use in lacustrine settings is sparse as their controls are not well-known. Previous studies in two lakes have shown that long-chain diol distribution is linked to changes in temperature (in a small Spanish alpine lake), but also to water column stratification (in a large deep Swiss lake). To understand the controls on i) the presence of long-chain diols in lakes, and ii) the distribution of long-chain diol isomers, surface sediments from 52 Swiss lakes were studied. Long-chain diols are present in 57% of the lakes, and machine learning (i.e., random forest model) showed that their presence is mainly controlled by mean annual air temperature, sodium and potassium concentrations and area of the lakes. Long-chain diol isomer relative distribution seems to react to temperature, nutrient (here nitrate) and oxygen concentrations in the lakes. This new insight was tested on a short sedimentary core from Lake Zurich, and compared with other biomarker proxies (based on branched and isoprenoid glycerol dialkyl glycerol tetraethers), as well as with historical record of nutrient contents and temperature. Variations in the long-chain diol index (LDI) mirror measured temperature, but also reacted to changes in nutrients and oxygenation in the lake. This study highlights the potential of long-chain diols as a proxy to trace both nutrients and temperature in lakes, potentially on geological timescales.

Intensified bacterial productivity during the Paleocene–Eocene thermal maximum: Molecular evidence in the Tarim Basin in the eastern Tethyan realm

The investigation of bulk and molecular compositions in organic matter at the Bashibulake Section in the SW Tarim Basin, West China, across the Paleocene–Eocene boundary reveals a complex mixture of marine and terrigenous origins during the Paleocene–Eocene Thermal Maximum (PETM) in the eastern Tethys. Source-related biomarkers, such as n-alkanes, isoprenoid alkanes, steranes, hopanes and methylhopanes, exhibit diverse compositions influenced by both marine and terrigenous sources. Sterane and hopane isomer distributions, indicative of immature OM, are primarily controlled by biological configurations. Changes in compound class abundance and isomer ratios reflect variations in source inputs and depositional conditions. Elevated concentrations of n-alkanes from higher plants, along with ratios of C29-C32 moretanes/hopanes and C31/C32 homohopanes, suggest increased terrigenous OM supply during the PETM. However, the significant differences in concentration between n-alkanes from higher land plants and bacterial hopanes, coupled with the presence of 2α-methylhopanes, prevalence of C27 compounds in regular steranes, and absence of oleanane suggest a dominant aquatic bacterial contribution. The study highlights the role of enhanced continental flux and warming in stimulating microbial activity, enriching OM, a factor often overlooked by other analytical methods. The absence of carbonate carbon and low trisnorhopane isomerization provide supportive evidence of ocean acidification and carbonate dissolution during the PETM. Reduced pregnanes and tricyclic terpanes, along with low degree of hopane and sterane isomerization, indicate rising sea levels and low salinity. The findings emphasize the significance of the biomarker approach in identifying OM origin and characterizing the depositional environment in PETM-related sequences, suggesting a more substantial role of bacterial contributions than previously recognized.

Hydrogen Tag Shifts as Vibrational Reporters for Positional Isomers of Formylphenides: Surprising Mobility of the Carbanion Center upon Collisional Decarboxylation of the Parent Benzoates.

Infrared photodissociation of weakly bound "mass tags" is widely used to determine the structures of ions by analyzing their vibrational spectra. Molecular hydrogen is a common choice for tagging in cryogenic radio-frequency ion traps. Although the H2 molecules can introduce distortions in the target species, we demonstrate an advantage of H2 tagging in the analysis of positional isomers adopted by the molecular anions derived from decarboxylation of formylbenzoates. Attachment of H2 to the carbanion centers of three such isomers yields distinct shifts in the H2 stretch, which can be used to determine the distribution of isomers in an unknown sample. Electronic structure calculations indicate that the position-dependent shifts are due to different reactivities of the carbanion sites with respect to an intracluster proton-transfer reaction with the H2 molecule. We exploit this spectroscopic method to quantify the surprisingly facile migrations of the anionic center that have been previously reported for phenide rearrangements.

Unraveling the potential of backbone modifications in iron(II) NHC complexes for olefin aziridination and imination

A model catalysis reaction for a C2 + N1 type aziridination and imination of p-tolyl azide with cis-cyclooctene in toluene is reported. Applying 10 equivalents related to the azide, cis-cyclooctene is consumed within 24 h. A reaction temperature of 90 °C is chosen for solubility and activity reasons. A variety of Fe(II) N-heterocyclic carbene (NHC) complexes (1–5) are tested as additives. All show promising formation of aziridine and its imine isomer in the benchmark reaction. However, similar activities are also achieved by a metal-free control reaction together with a similar product distribution of A (aziridine), B (imine) and C (aziridine). The metal compounds cannot be considered as catalysts, but they do indeed influence the isomeric distribution of the reaction. To contextualize the conceivable product isomers, density functional theory calculations were performed (B3LYP/6–31G(d,p)) to determine the minimum ground state energies. As expected, these are nearly identical. However, the backbone modification of the open-chain NHC ligated iron(II) complex (5) allows switching of the predominant reaction, favoring imine (B) as main product.

Study on the preparation and n-heptane isomerization performance of MoOx-Pd/Ce-MCM-48 catalyst.

A Ce-MCM-48 molecular sieve was prepared by the hydrothermal synthesis method. Using Ce-MCM-48 as the support, a series of MoOx Pd/Ce-M catalysts were prepared by the impregnation method by introducing MoOx and Pd. XRD, N2 adsorption desorption, SEM, TEM, NH3-TPD, Py-IR, FT-IR, and ICP-MS were used to characterize the physicochemical properties. The performance of n-heptane isomerization in a micro fixed bed device was evaluated. The results showed that the synthesized Ce-MCM-48 was mesoporous, with a spherical particle morphology, a long-range ordered pore structure, weakly acidic sites on the surface, and an increase of B and L acids. The 2% MoOx-Pd/Ce-M catalyst was used for the probe reaction of n-heptane hydroisomerization; when the reduction temperature was 400 °C, the reduction time was 2 hours, the reaction temperature was 300 °C, the WHSV was 7.6 h-1, the conversion rate was 58.7%, the selectivity was 91.2%, and the maximum yield was 53.5%. The product distribution of multiple C7 isomers increased the selectivity of multi branched isoheptane. The addition of an appropriate amount of MoOx would improve the performance of n-heptane isomerization.

Cyclic ion mobility of doped [MAu24L18]2- superatoms and their fragments (M = Ni, Pd and Pt; L = alkynyl).

Collision-induced dissociation and high-resolution cyclic ion mobility mass spectrometry, along with quantum chemical calculations and trajectory simulations, were used to compare the structures of isolated [MAu24(CCR)18]2-, M = Ni, Pd, or Pt, and their associated fragment ions. The three different alkynyl ligand-stabilized (CCR, R = 3,5-(CF3)2C6H3), transition metal-doped, gold cluster dianions showed mutually resolvable collision cross sections (CCS), which were ordered consistently with their molecular structures from X-ray crystallography. All three [MAu24(CCR)18]2- species fragment by sequential diyne loss to form [MAu24(CCR)18-n]2-, with n up to 12. The resultant fragment isomer distributions are significantly n- and M-dependent, and hint at a process involving concerted elimination of adjacent ligands. In particular [NiAu24(CCR)18]2- also fragments to generate alkyne-oligomers, an inference supported by the parallel observation of precursor dianion isomerization as collision energy is increased.

In-Depth Structure and Function Characterization of Heterogeneous Interchain Cysteine-Conjugated Antibody-Drug Conjugates.

Antibody-drug conjugates (ADCs), integrating high specificity of antigen-targeting antibodies and high potency of cell-killing chemical drugs, have become one of the most rapidly expanding therapeutic biologics in oncology. Although ADCs were widely studied from multiple aspects, overall structural elucidation with comprehensive understanding of variants is scarcely reported. Here, for the first time, we present a holistic and in-depth characterization of an interchain cysteine-conjugated ADC, focusing on conjugation and charge heterogeneity, and in vitro biological activities. Conjugation mapping utilized a bottom-up approach, unraveled positional isomer composition, provided insights into the conjugation process, and elucidated how conjugation affects the physicochemical and biological properties of an ADC. Charge profiling combined bottom-up and top-down approaches to interrogate the origin of charge heterogeneity, its impact on function, and best practice for characterization. Specifically, we pioneered the utilization of capillary isoelectric focusing-mass spectrometry to decode not only critical post-translational modifications but also drug load and positional isomer distribution. The study design provides general guidance for in-depth characterization of ADCs, and the analytical findings in turn benefit the discovery and development of future ADCs.

Tissue-specific distribution and bioaccumulation of perfluoroalkyl acids, isomers, alternatives, and precursors in citrus trees of contaminated fields: Implication for risk assessment

The ingestion of fruits containing perfluoroalkyl acids (PFAAs) presents potential hazards to human health. This study aimed to fill knowledge gaps concerning the tissue-specific distribution patterns and bioaccumulation behavior of PFAAs and their isomers, alternatives, and precursors (collectively as per-/polyfluoroalkyl substances, PFASs) within citrus trees growing in contaminated fields. It also assessed the potential contribution of precursor degradation to human exposure risk of PFASs. High concentrations of total target PFASs (∑PFASstarget, 92.45–7496.16 ng/g dw) and precursors measured through the total oxidizable precursor (TOP) assay (130.80–13979.21 ng/g dw) were found in citrus tree tissues, and short-chain PFASs constituted the primary components. The total PFASs concentrations followed the order of leaves > fruits > branches, bark > wood, and peel > pulp > seeds. The average contamination burden of peel (∑PFASstarget: 57.75%; precursors: 71.15%) was highest among fruit tissues. Bioaccumulation factors (BAFs) and translocation potentials of short-chain, branched, or carboxylate-based PFASs exceeded those of their relatively hydrophobic counterparts, while ether-based PFASs showed lower BAFs than similar PFAAs in above-ground tissues of citrus trees. In the risk assessment of residents consuming contaminated citruses, precursor degradation contributed approximately 36.07% to total PFASs exposure, and therefore should not be ignored.

Impact of aerobic reworking of biomass on steroid and hopanoid biomarker parameters recording ecological conditions and thermal maturity

Steranes and hopanes are the biomarkers of eukaryotic sterols and bacterial hopanols. Extracted from sedimentary rock, they are widely used to assess burial temperatures and palaeoecological conditions. The relative proportion of steranes and hopanes is commonly applied as a measure of the flux of eukaryotic versus bacterial biomass into sediments, and the relative abundances of C27, C28 and C29 steranes are proxies for shifts in eukaryote ecology. In Recent sediments, intact sterols provide additional information about particular eukaryotic origins. However, biological lipid distributions are not always recorded faithfully in sediments. Based on observations on modern algae and plants, and on 558 million year old fossil macroalgae from the Ediacaran of the White Sea, we suggest that these biomarker proxies can be severely altered by aerobic microbial reworking, to the extent that a complete loss of primary ecological information may occur. Network analysis on the biomarker data suggests that oxic degradation also affects isomer and homolog distributions of saturated and aromatic steroids, hopanes, cheilanthanes and n-alkanes, generating anomalies in apparent thermal maturity indicators and other proxies. In our dataset, between Ediacaran macroalgae that experienced the least and the most oxic degradation, the absolute concentration of biomarkers decreases 80-fold, and at the same time the proportion of steranes over hopanes decreases by a factor of 82, while the proportion of C29 steranes among total steranes decreases from 91% to 47%. Such redox dependent offsets may explain the recurrently erratic behaviour of numerous biomarker parameters. While these results impart constraints on the interpretation of biomarker distributions, they do provide a tool for evaluating the effects of oxygen exposure and microbial degradation on organic matter preservation in recent and ancient environments and may point towards a solution for the correction of such effects.

The distribution and metabolism of hexabromocyclododecane isomers varies in the tissues of Nibea albiflora

Hexabromocyclododecanes (HBCDs), as brominated flame retardants, have increasingly drawn concern due to their detection in various marine organisms in recent years. The present test investigated the selective accumulation, depuration, and bioisomerization of HBCDs in different tissues and organs of Nibea albiflora, as well as the genetic metabolic behavior of HBCDs between parents and offspring. In a semi-static water environment, N. albiflora were exposed to individual HBCD diastereoisomers (α-HBCD, β-HBCD, or γ-HBCD) at a concentration of 0.4 μg/L for bioaccumulation, followed by clean food for depuration. During the exposure period, the highest concentrations of these HBCDs were observed in the intestine and gill of N. albiflora. α-HBCD was detected in all exposure groups, suggesting that both β-HBCD and γ-HBCD could be bioisomerized to α-HBCD in N. albiflora. In addition, there was no bioisomerization of α-HBCD to either β-HBCD or γ-HBCD, and there was no bioisomerization between β-HBCD and γ-HBCD. The half-lives (t1/2) were variable among different diastereoisomers, following an order of α-HBCD > γ-HBCD > β-HBCD. The most rapid depuration rate of HBCDs was discovered in the liver while muscle showed the least. Additionally, prior to spawning, the parent fish were exposed to contaminated feed (silkworms sprayed with 200 μL of a 30 μg/mL HBCD solution) for 6 days. By comparing the HBCDs concentrations in the maternal gonad, fertilized eggs, hatching eggs, larvae, and juveniles, it was determined that the maternal transfer coefficients for HBCDs were approximately 1, indicating dynamic equilibrium of HBCDs throughout the process from maternal tissue to progeny development. Differences in HBCDs pattern between organs observed in the experiment support a proposal of an organ-specific diastereomer accumulation.

Revealing Structure and Localization of Steroid Regioisomers through Predictive Fragmentation Patterns in Mass Spectrometry Imaging.

Identifying and mapping steroids in tissues can provide opportunities for biomarker discovery, the interrogation of disease progression, and new therapeutics. Although separation coupled to mass spectrometry (MS) has emerged as a powerful tool for studying steroids, imaging and annotating steroid isomers remains challenging. Herein, we present a new method based on the fragmentation of silver-cationized steroids in tandem MS, which produces distinctive and consistent fragmentation patterns conferring confidence in steroid annotation at the regioisomeric level without using prior derivatization, separation, or instrumental modification. In addition to predicting the structure of the steroid with isomeric specificity, the method is simple, flexible, and inexpensive, suggesting that the wider community will easily adapt to it. We demonstrate the utility of our approach by visualizing steroids and steroid isomer distributions in mouse brain tissue using silver-doped pneumatically assisted nanospray desorption electrospray ionization mass spectrometry imaging.

The influence of asphaltene matrix on the thermal evolution of polycyclic aromatic hydrocarbons: Experimental evidence and geochemical implications

The thermal evolution of components trapped in matrix of asphaltenes is supposed to be retarded, as compared to the free ones. Studying the geochemical evolution of trapped polycyclic aromatic hydrocarbons (PAHs) may provide insight for the characterization of high-maturity organic matter. The discrepancies in the thermal evolution between free and trapped (asphaltene-adsorbed/occluded) PAHs (phenanthrene, chrysene, pyrene, and their methylated isomers) were studied by thermal maturation (gold tubes, 300 ∼ 400 °C) experiments on a low-maturity solid bitumen from the Sichuan Basin, southwestern China. The results show that the thermal evolution of asphaltene-adsorbed PAHs is retarded compared to that of free ones. This is attributed to slight differences in reaction kinetics due to steric hindrance by the asphaltene structure. The asphaltene matrix appears to act as a reaction inhibitor leading to a retardation of the thermal evolution of the methylphenanthrene index (MPI) in asphaltene-adsorbed hydrocarbons. This could provide a possibility for maturity assessment of high-maturity organic matter. The thermal evolution of asphaltene-occluded PAHs in the experiments resulted in thermodynamically controlled isomer distributions of occluded methylphenanthrenes and methylchrysenes. However, the occluded methylpyrene isomers were hardly affected by thermal stress. They probably retained their original distributions and may serve as source indicators.

Mechanistic aspects of n-hexadecane hydroconversion: Impact of di-branched isomers on the cracked products distribution

The mechanism of n-hexadecane (n-C16) hydroisomerization/hydrocracking was studied over bifunctional catalysts employing Pd and Pt as (de)hydrogenation components and large-pore zeolites and (ordered) mesoporous materials as acidic supports. Zeolite Y and Beta supports were compared to amorphous silica-alumina as well as aluminium-containing ordered mesoporous MCM-41, MCM-48 and SBA-15 materials to cover a wide range of pore sizes and topologies. Products were analyzed in terms of mono- and di-branched C16 isomers and cracked products as a function of the n-C16 conversion. All samples followed a similar mechanism in which, at low conversion, di-branched isomers with methyl groups toward the ends of the tetradecane chain were observed. At higher conversion, the products shifted to isomers with methyl groups closer to the center at higher n-C16 conversion. Consistent with these differences, the typical ‘M’ shape distribution of cracked products was obtained at low conversion, which evolved into ideal symmetric cracking patterns at higher conversion. The unusual di-branched isomer distribution at low conversion and the corresponding ‘M’ shaped cracked products distribution have earlier been associated with pore mouth catalysis induced by restricted diffusion in medium-pore zeolites. Here we show that such reaction pathways also occur in catalysts with large enough pores to exclude diffusion restrictions.

In situ separation and visualization of isomeric auxin derivatives in Arabidopsis by ion mobility mass spectrometry imaging.

In situ separation and visualization of synthetic and naturally occurring isomers from heterogeneous plant tissues, especially when they share similar molecular structures, are a challenging task. In this study, we combined the ion mobility separation with desorption electrospray ionization mass spectrometry imaging (DESI-IM-MSI) to achieve a direct separation and visualization of two synthetic auxin derivatives, auxinole and its structural isomer 4pTb-MeIAA, as well as endogenous auxins from Arabidopsis samples. Distinct distribution of these synthetic isomers and endogenous auxins in Arabidopsis primary roots and hypocotyls was achieved in the same imaging analysis from both individually treated and cotreated samples. We also observed putative metabolites of synthetic auxin derivatives, i.e. auxinole amino acid conjugates and hydrolysed 4pTb-MeIAA product - 4pTb-IAA, based on their unique drifting ion intensity patterns. Furthermore, DESI-IM-MSI-revealed abundance of endogenous auxins and synthetic isomers was validated by liquid chromatography-mass spectrometry (LC-MS). Our results demonstrate that DESI-IM-MSI could be used as a robust technique for detecting endogenous and exogenous isomers and provide a spatiotemporal evaluation of hormonomics profiles in plants.

In-depth profiling of carbohydrate isomers in biological tissues by chemical derivatization-assisted mass spectrometry imaging

Carbohydrates play crucial regulatory roles in various physiological and pathological processes. However, the low ionization efficiency and the presence of linkage pattern, monosaccharide composition and anomeric configuration isomers make their in-depth analysis very challenging, especially for heterogeneous biological tissues. In this study, we propose a high-sensitive and isomer-specific imaging approach to visualize the spatial distributions of monosaccharide and disaccharide isomers by integrating chemical derivatization and matrix-assisted laser desorption/ionization tandem mass spectrometry imaging (MALDI-MS2I). 2-Pyridinecarbohydrazide (PYD) is developed as a novel derivatization reagent which can not only improves the MS sensitivity of carbohydrates, but also enables the identification and visualization of ketose and aldose monosaccharide isomers, as well as linkage pattern, monosaccharide composition and anomeric configuration disaccharide isomers by mass spectrometry imaging of isomer-specific MS/MS fragment ions. Moreover, we build quantitative MALDI-MS2 and MALDI-MS2I methods for disaccharide isomers based on the diagnostic fragment ions, and good linear relationships could be achieved both in solution and on glass slides. We expect that this study should provide new ideas for in-depth profiling of the spatial signatures of carbohydrates in biological tissues and lay the foundation for a deeper understanding of carbohydrates’ structure.