Browse
Submit Data
Databases
API
Help

Dataset Information

24 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Base-Assisted Conversion of Protonated d-Fructose to 5-HMF: Searching for Gas-Phase Green Models.

ABSTRACT: A gas-phase investigation of the d-fructose dehydration reaction in the presence of base has been performed by the joint application of mass spectrometric techniques and theoretical calculations. Protonated addition products of d-fructose and base were generated in the gas phase by electrospray ionization using several bases of different proton affinity. The intermediates, products and decomposition channels were investigated by ion trap mass spectrometry. Electronic structure calculations allowed the identification of the ionic intermediates and products of a selected system containing NH₃, helping to rationalize the observed reaction pathways. The obtained results show that the final product, the protonated 5-hydroxymethyl-2-furaldheyde [5-HMF]H⁺, is better formed using selected bases and only if these remain clustered until the end of the dehydration process.

SUBMITTER: Troiani A

PROVIDER: S-EPMC6723769 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Base-Assisted Conversion of Protonated d-Fructose to 5-HMF: Searching for Gas-Phase Green Models.

Troiani Anna A de Petris Giulia G Pepi Federico F Garzoli Stefania S Salvitti Chiara C Rosi Marzio M Ricci Andreina A

ChemistryOpen 20190904 9

A gas-phase investigation of the d-fructose dehydration reaction in the presence of base has been performed by the joint application of mass spectrometric techniques and theoretical calculations. Protonated addition products of d-fructose and base were generated in the gas phase by electrospray ionization using several bases of different proton affinity. The intermediates, products and decomposition channels were investigated by ion trap mass spectrometry. Electronic structure calculations allow ...[more]

PMID: 31508268

Similar Datasets

Catalytic Dehydration of Fructose to 5-Hydroxymethylfurfural (HMF) in Low-Boiling Solvent Hexafluoroisopropanol (HFIP).

Project description:A mixture of hexafluoroisopropanol (HFIP) and water was used as a new and unknown monophasic reaction solvent for fructose dehydration in order to produce HMF. HFIP is a low-boiling fluorous alcohol (b.p. 58 °C). Hence, HFIP can be recovered cost efficiently by distillation. Different ion-exchange resins were screened for the HFIP/water system in batch experiments. The best results were obtained for acidic macroporous ion-exchange resins, and high HMF yields up to 70% were achieved. The effects of various reaction conditions like initial fructose concentration, catalyst concentration, water content in HFIP, temperature and influence of the catalyst particle size were evaluated. Up to 76% HMF yield was attained at optimized reaction conditions for high initial fructose concentration of 0.5 M (90 g/L). The ion-exchange resin can simply be recovered by filtration and reused several times. This reaction system with HFIP/water as solvent and the ion-exchange resin Lewatit K2420 as catalyst shows excellent performance for HMF synthesis.

| S-EPMC6222439 | biostudies-literature

Intrinsic photoisomerization dynamics of protonated Schiff-base retinal.

Project description:The retinal protonated Schiff-base (RPSB) in its all-trans form is found in bacterial rhodopsins, whereas visual rhodopsin proteins host 11-cis RPSB. In both cases, photoexcitation initiates fast isomerization of the retinal chromophore, leading to proton transport, storage of chemical energy or signaling. It is an unsolved problem, to which degree this is due to protein interactions or intrinsic RPSB quantum properties. Here, we report on time-resolved action-spectroscopy studies, which show, that upon photoexcitation, cis isomers of RPSB have an almost barrierless fast 400 fs decay, whereas all-trans isomers exhibit a barrier-controlled slow 3 ps decay. Moreover, formation of the 11-cis isomer is greatly favored for all-trans RPSB when isolated. The very fast photoresponse of visual photoreceptors is thus directly related to intrinsic retinal properties, whereas bacterial rhodopsins tune the excited state potential-energy surface to lower the barrier for particular double-bond isomerization, thus changing both the timescale and specificity of the photoisomerization.

| S-EPMC6418104 | biostudies-literature

Efficient Conversion of Glucose into Fructose via Extraction-Assisted Isomerization Catalyzed by Endogenous Polyamine Spermine in the Aqueous Phase.

Project description:In the present study, natural polyamine spermine is demonstrated as a potential basic catalyst for glucose-to-fructose isomerization. For instance, spermine achieves a decent fructose yield (30% wt) and selectivity (74%) during the single-step aqueous phase isomerization under the modest operating conditions (100 °C for 15 min). In addition to the expected reaction byproduct monosugar mannose, spermine also assists in the synthesis of rare and important monosugar, that is, psicose up to 4% wt. Psicose is a zero calorie rare sugar, exhibits a low caloric value, and possesses anti-adipogenic property. A comparative study involving other polyamines concluded that the presence of 20 amines tends to exhibit the most significant impact in improving the target product yield by releasing a higher number of OH- ions, which are responsible for isomerization through the formation of an enediol anion. An attempt was made to further improve the fructose yield through the addition of neutral salts, but it promoted a meager achievement. In an alternate study, a selective extraction strategy was followed for the isolation of fructose from the reaction mixture. The employed aryl monoboronic acid remarkably improved the net fructose concentration, that is, fructose productivity up to 75% wt (cumulative) and 70% selectivity within three consecutive extractions and isomerization cycles, which is comparatively three times shorter than that reported in the literature. Notably, spermine itself provided the essential and necessary basic environment for selective fructose extraction and glucose isomerization, ruling out the use of any external reagents and thus establishing itself as a versatile material suitable for a typical isomerization reaction in an upscaled reactor.

| S-EPMC7017403 | biostudies-literature

Retinal conformation governs pKa of protonated Schiff base in rhodopsin activation.

Project description:We have explored the relationship between conformational energetics and the protonation state of the Schiff base in retinal, the covalently bound ligand responsible for activating the G protein-coupled receptor rhodopsin, using quantum chemical calculations. Guided by experimental structural determinations and large-scale molecular simulations on this system, we examined rotation about each bond in the retinal polyene chain, for both the protonated and deprotonated states that represent the dark and photoactivated states, respectively. Particular attention was paid to the torsional degrees of freedom that determine the shape of the molecule, and hence its interactions with the protein binding pocket. While most torsional degrees of freedom in retinal are characterized by large energetic barriers that minimize structural fluctuations under physiological temperatures, the C6-C7 dihedral defining the relative orientation of the ?-ionone ring to the polyene chain has both modest barrier heights and a torsional energy surface that changes dramatically with protonation of the Schiff base. This surprising coupling between conformational degrees of freedom and protonation state is further quantified by calculations of the pKa as a function of the C6-C7 dihedral angle. Notably, pKa shifts of greater than two units arise from torsional fluctuations observed in molecular dynamics simulations of the full ligand-protein-membrane system. It follows that fluctuations in the protonation state of the Schiff base occur prior to forming the activated MII state. These new results shed light on important mechanistic aspects of retinal conformational changes that are involved in the activation of rhodopsin in the visual process.

| S-EPMC5176254 | biostudies-literature

Solid base catalysed 5-HMF oxidation to 2,5-FDCA over Au/hydrotalcites: fact or fiction?

Project description:Nanoparticulate gold has emerged as a promising catalyst for diverse mild and efficient selective aerobic oxidations. However, the mechanism of such atom-economical transformations, and synergy with functional supports, remains poorly understood. Alkali-free Mg-Al hydrotalcites are excellent solid base catalysts for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furan dicarboxylic acid (FDCA), but only in concert with high concentrations of metallic gold nanoparticles. In the absence of soluble base, competitive adsorption between strongly-bound HMF and reactively-formed oxidation intermediates site-blocks gold. Aqueous NaOH dramatically promotes solution phase HMF activation, liberating free gold sites able to activate the alcohol function within the metastable 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) reactive intermediate. Synergistic effects between moderate strength base sites within alkali-free hydrotalcites and high gold surface concentrations can afford highly selective and entirely heterogeneous catalysts for aqueous phase aldehyde and alcohol cascade oxidations pertinent to biomass transformation.

| S-EPMC6088438 | biostudies-literature

Widespread distribution of <i>hmf</i> genes in Proteobacteria reveals key enzymes for 5-hydroxymethylfurfural conversion.

Project description:Furans represent a class of promising chemicals, since they constitute valuable intermediates in conversion of biomass into sustainable products intended to replace petroleum-derivatives. Conversely, generation of furfural and 5-hydroxymethylfurfural (HMF) as by-products in lignocellulosic hydrolysates is undesirable due its inhibitory effect over fermentative microorganisms. Therefore, the search for furans-metabolizing bacteria has gained increasing attention since they are valuable tools to solve these challenging issues. A few bacterial species have been described at genetic level, leading to a proposed HMF pathway encoded by a set of genes termed hmf/psf, although some enzymatic functions are still elusive. In this work we performed a genomic analysis of major subunits of furoyl-CoA dehydrogenase orthologues, revealing that the furoic acid catabolic route, key intermediate in HMF biodegradation, is widespread in proteobacterial species. Additionally, presence/absence profiles of hmf/psf genes in selected proteobacterial strains suggest parallel and/or complementary roles of enzymes with previously unclear function that could be key in HMF conversion. The furans utilization pattern of selected strains harboring different hmf/psf gene sets provided additional support for bioinformatic predictions of the relevance of some enzymes. On the other hand, at least three different types of transporter systems are clustered with hmf/psf genes, whose presence is mutually exclusive, suggesting a core and parallel role in furans transport in Proteobacteria. This study expands the number of bacteria that could be recruited in biotechnological processes for furans biodetoxification and predicts a core set of genes required to establish a functional HMF pathway in heterologous hosts for metabolic engineering endeavors.

| S-EPMC8091172 | biostudies-literature

Characterization of Conformational Ensembles of Protonated N-glycans in the Gas-Phase.

Project description:Ion mobility mass spectrometry (IM-MS) is a technique capable of investigating structural changes of biomolecules based on their collision cross section (CCS). Recent advances in IM-MS allow us to separate carbohydrate isomers with subtle conformational differences, but the relationship between CCS and atomic structure remains elusive. Here, we characterize conformational ensembles of gas-phase N-glycans under the electrospray ionization condition using molecular dynamics simulations with enhanced sampling. We show that the separation of CCSs between isomers reflects folding features of N-glycans, which are determined both by chemical compositions and protonation states. Providing a physicochemical basis of CCS for N-glycans helps not only to interpret IM-MS measurements but also to estimate CCSs of complex glycans.

| S-EPMC5786100 | biostudies-literature

High-Yield and High-Efficiency Conversion of HMF to Levulinic Acid in a Green and Facile Catalytic Process by a Dual-Function Bronsted-Lewis Acid HScCl<sub>4</sub> Catalyst.

Project description:Lignocellulosic biorefineries have received considerable attention for the purpose of producing high-value chemicals and materials. Levulinic acid (LA) is an important biomass-derived platform chemical that is produced from sugar-based biomass. Unfortunately, the catalysts reported thus far have shortcomings, such as expensive starting materials, complicated synthesis or purification operations, and a low LA yield under harsh reaction conditions. Herein, we develop a novel dual-functional catalyst, HScCl4, by combining Brønsted acid (HCl) and Lewis acid (ScCl3) sites. The as-prepared HScCl4 catalyst shows high efficiency and high selectivity for converting 5-hydroxymethylfurfural (HMF) to LA in a biphasic system consisting of methyl isobutyl ketone (MIBK) and water. The density functional theory (DFT) results show that the synergistic catalytic effect, originating from the Brønsted and Lewis acidic sites of HScCl4, significantly decreases the energy barriers of reactants and intermediates, thus facilitating the conversion of HMF to LA. Moreover, the efficient separation of LA in the water-MIBK biphasic system by extracting LA to the MIBK phase minimizes the side reactions of LA and thus the formation of humins while significantly improving the LA yield. The conversion of HMF and the selectivity for LA are 100 and 95.6% at 120 °C for 35 min, respectively. The free energy (ΔG) and activation energy (E a) of the reaction are -30 kcal mol-1 and 13.7 kJ mol-1, respectively. The developed process provides a green, sustainable, and efficient pathway to produce LA from biomass-derived HMF under mild conditions.

| S-EPMC8223403 | biostudies-literature

Gas-phase bioconjugation of peptides via ion/ion charge inversion: Schiff base formation on the conversion of cations to anions.

Project description:The selective covalent modification of singly protonated peptides in the gas-phase via ion/ion charge inversion reactions is demonstrated. Doubly deprotonated 4-formyl-1,3-benzene disulfonic acid serves as a reagent anion for forming a Schiff base via the reaction of a primary amine on the peptide and the aldehyde functionality of the reagent anion. The process is initiated by the formation of an ion/ion complex comprised of the two reactants. Ion trap collisional activation of the complex results in loss of water from the intermediate that gives rise to Schiff base formation. N-terminally acetylated peptides with no lysine residues do not undergo covalent bond formation upon reaction with the reagent anion. Rather, the adduct species simply loses the reagent either as a neutral species or as a deprotonated species. The ability to modify singly protonated peptide ions covalently and selectively opens up new possibilities for the analysis of peptides and, possibly, other analyte species with primary amine functionalities.

| S-EPMC2834292 | biostudies-literature

Green and Efficient Extraction Approach for Polyphenol Recovery from Lotus Seedpods (Receptaculum Nelumbinis): Gas-Assisted Combined with Glycerol.

Project description:In this paper, the gas-assisted combined with glycerol extraction (GAGE) for polyphenol recovery from lotus seedpods (LSPs) was modeled and optimized. Box-Behnken design was applied to optimize the total polyphenol content (TPC) of LSP along with enhancing antioxidant activities using response surface methodology based on the TPC extraction yield (%), which was affected by glycerol concentration, time, temperature, and glycerol-to-solid ratio. The optimal conditions for the LSP extract were glycerol-to-solid ratio, 42 mL/g; time, 50 min; concentration of glycerol, 45%; and temperature, 70 °C. Ultra-high-pressure liquid chromatography integrated with triple-time-of-flight mass spectrophotometry (UPLC-Triple-TOF/MS) analysis revealed nine biologically active polyphenols. Furthermore, Fourier-transform infrared spectroscopy and scanning electron microscopy results demonstrated the effect and influence during extraction. The findings suggested that GAGE is a potential, green, and high-efficiency alternative that could be used to recover polyphenols from plant source byproducts.

| S-EPMC8515820 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data