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1.
Anal Chim Acta ; 1157: 338401, 2021 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-33832583

RESUMO

Unified chromatography with mass spectrometric detection was assessed for determination of food dyes. Nineteen substances representing azo, triphenylmethane, xanthone, indigoid, quinoline and polyene classes covering an unprecedented range from nonpolar ß-Carotene (logD 13.6) to ionic Tartrazine (logD -7.5) were analyzed simultaneously. The dyes were separated in a single experimental run by an 18-min gradient elution from 98% CO2 to 100% aqueous-methanolic modifier on a diol column. Isomeric substances were resolved, and Isatin Sulfonic acid was detected as a degradation product of Indigo Carmine. Mobile phase properties reproducibly changed from supercritical to liquid state ensuring stable retention times (inter-day RSD<0.5%). Quantitative analysis of sports drinks after straightforward 10- or 25-fold dilution with dimethyl sulfoxide confirmed the method applicability to real-life samples. Sufficient limits of detection (typically 0.025 mg L-1 in processed samples, equivalent to 0.25 mg L-1 in drink) and a wide linear range (typically 0.5-50 mg L-1 or 1.3-125 mg L-1 in drink for 10× or 25× dilution, respectively) were demonstrated during validation. A comparison of method performance with competitive liquid chromatography procedures is also provided. Unified chromatography is a promising tool for comprehensive multiclass analysis of dyes in the context of food safety.

2.
J Am Soc Mass Spectrom ; 32(4): 1041-1052, 2021 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-33655750

RESUMO

Diazirine-tagged d- and l-adrenaline derivatives formed abundant noncovalent gas-phase ion complexes with peptides N-Ac-SSIVSFY-NH2 (peptide S) and N-Ac-VYILLNWIGY-NH2 (peptide V) upon electrospray ionization. These peptide sequences represent the binding motifs in the ß2-adrenoreceptor. The structures of the gas-phase complexes were investigated by selective laser photodissociation of the diazirine chromophore at 354 nm, which resulted in a loss of N2 and formation of a transient carbene intermediate in the adrenaline ligand without causing its expulsion. The photolyzed complexes were analyzed by collision-induced dissociation (CID-MS3 and CID-MS4) in an attempt to detect cross-links and establish the binding sites. However, no cross-linking was detected in the complexes regardless of the peptide and d- or l-configuration in adrenaline. Cyclic ion mobility measurements were used to obtain collision cross sections (CCS) in N2 for the peptide S complexes. These showed identical values, 334 ± 0.9 Å2, for complexes of the l- and d-adrenaline derivatives, respectively. Identical CCS were also obtained for peptide S complexes with natural l- and d-adrenaline, 317 ± 1.2 Å2, respectively. Born-Oppenheimer molecular dynamics (BOMD) in combination with full geometry optimization by density functional theory calculations provided structures for the complexes that were used to calculate theoretical CCS with the ion trajectory method. A close match (337 Å2) was found for a single low Gibbs energy structure that displayed a binding pocket with Ser 2 and Ser 5 residues forming hydrogen bonds to the adrenaline catechol hydroxyls. Analysis of the BOMD trajectories revealed a small number of contacts between the incipient carbene carbon atom in the ligand and X-H bonds in the peptide, which was consistent with the lack of cross-linking. Temperature dependence of the internal dynamics of peptide S-adrenaline complexes as well as the specifics of the adrenaline carbene reactions are discussed. In particular, peptide amide hydrogen transfer to the carbene carbon atom was calculated to require crossing a potential energy barrier, which may hamper cross-linking in competition with carbene internal rearrangements.

3.
Carbohydr Polym ; 250: 117014, 2020 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-33049874

RESUMO

The aim of this paper is to review chromatographic and mass-spectrometric methods and underline the best analytical approaches for successful analysis of various hyaluronic acid species in different types of samples. Hyaluronan-degrading enzymes and chemical depolymerization produce di- or oligosaccharides suitable for hyaluronan quantification or structural characterization of hyaluronan derivatives. Efficient purification and pre-column derivatization of hyaluronan disaccharides by reductive amination allow subnanogram quantification in biological samples. The chromatographic separation is capable to distinguish all glycosaminoglycans disaccharides and to resolve hyaluronan fragments with 2-40 monomers. Using electrospray ionization or matrix assisted laser desorption ionization, hyaluronan fragments up to 8 kDa or 41 kDa, respectively, can be observed. One- or two-dimensional chromatographic separation with higly sensitive mass-spectrometric detection is an indispensable tool for revealing substituent position, extent of modification and substitution patterns of chemically modified hyaluronan derivatives. It is essential for studying structure-biological function relationships of hyaluronan and its derivatives.

4.
J Mass Spectrom ; 55(10): e4642, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32910468

RESUMO

The efficiency of desorption/ionization becomes more critical as the sampled surface area decreases. Desorption electrospray and desorption nanoelectrospray belong to ambient ionizations and enable direct surface analysis including mass spectrometric imaging. Lateral resolution in tens of micrometers was demonstrated for desorption nanoelectrospray previously, but sensitivity of the surface scan can be an issue. For desorption electrospray, the drag force in the source is driven by the flow of used gases and vacuum suction. Ion signal intensity can be improved by controlling the nebulizing gas flow rate or auxiliary pumping of a closed compartment in front of the mass spectrometer inlet. Because nanoelectrospray generates charged droplets without the assistance of a nebulizing gas, only vacuum suction drives the gas flow. In this study, the effect of pressure drop between the atmospheric and evacuated region of a mass spectrometer on the ion signal intensity was investigated for desorption nanoelectrospray. A modification of the commercial inlet was designed. An auxiliary pump was directly connected to an inner compartment of the modified mass spectrometer inlet through a needle valve that enabled the regulation of the reduced pressure. Adjustment of the pressure drop significantly increased signal intensity (more than one order of magnitude in some cases). To a lesser extent, the temperature of a heated capillary (an integral part of the inlet) also influenced the signal intensity. The applicability of desorption nanoelectrospray equipped with pressure regulation was demonstrated by the analysis of synthetic cathinones or a pill of paracetamol. Because pressure in the inlet depends on the diameters of orifices and the power of vacuum systems of mass spectrometers, the effect of the pressure regulation can be different for different instruments. Nevertheless, the presented results confirmed the importance of pressure drop-driven transport for desorption nanoelectrospray efficiency and can encourage its new applications.

5.
Sci Rep ; 10(1): 11447, 2020 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-32632189

RESUMO

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

6.
Sci Rep ; 10(1): 12356, 2020 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-32704032

RESUMO

We implement an all-optical setup demonstrating kernel-based quantum machine learning for two-dimensional classification problems. In this hybrid approach, kernel evaluations are outsourced to projective measurements on suitably designed quantum states encoding the training data, while the model training is processed on a classical computer. Our two-photon proposal encodes data points in a discrete, eight-dimensional feature Hilbert space. In order to maximize the application range of the deployable kernels, we optimize feature maps towards the resulting kernels' ability to separate points, i.e., their "resolution," under the constraint of finite, fixed Hilbert space dimension. Implementing these kernels, our setup delivers viable decision boundaries for standard nonlinear supervised classification tasks in feature space. We demonstrate such kernel-based quantum machine learning using specialized multiphoton quantum optical circuits. The deployed kernel exhibits exponentially better scaling in the required number of qubits than a direct generalization of kernels described in the literature.

7.
J Sep Sci ; 43(6): 1190-1194, 2020 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-31849194

RESUMO

Multimode ionization source allows for switching between different ionization techniques, for example, electrospray and atmospheric pressure chemical ionization, within a single analysis. Supercritical fluid chromatography can handle a wide polarity range of substances from hydrophilic to lipophilic in a single run and can undoubtedly benefit from versatility of this ion source. Nevertheless, we observed a significant chromatographic peak broadening effect in atmospheric pressure chemical ionization mode during supercritical fluid chromatography-mass spectrometry analysis of volatile flavor compounds with a dual ion source named ESCi (Waters). Surprisingly, this effect was not related to the separation process but was triggered solely by the ion source conditions. Neither of photodiode array detector, electrospray mode nor a dedicated atmospheric pressure chemical ionization source suffered from such a phenomenon. Chromatographic peak profiles of ten test substances obtained with the dual ion source were compared with photodiode array detector data as a reference. The broadening effect was more pronounced for volatile compounds with low polarity. Dependence of peak broadening on the ion source settings was systematically investigated. Tuning of desolvation gas flow and its temperature dramatically reduced peak distortion and increased detection sensitivity.

8.
Opt Express ; 27(22): 32454-32464, 2019 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-31684458

RESUMO

We report on experimental implementation of a machine-learned quantum gate driven by a classical control. The gate learns optimal phase-covariant cloning in a reinforcement learning scenario having fidelity of the clones as reward. In our experiment, the gate learns to achieve nearly optimal cloning fidelity allowed for this particular class of states. This makes it a proof of present-day feasibility and practical applicability of the hybrid machine learning approach combining quantum information processing with classical control. The quantum information processing performed by the setup is equivalent to boson sampling, which, in complex systems, is predicted to manifest quantum supremacy over classical simulation of linear-optical setups.

9.
Sci Rep ; 9(1): 16318, 2019 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-31704951

RESUMO

The concept of quantum money (QM) was proposed by Wiesner in the 1970s. Its main advantage is that every attempt to copy QM unavoidably leads to imperfect counterfeits. In the Wiesner's protocol, quantum banknotes need to be delivered to the issuing bank for verification. Thus, QM requires quantum communication which range is limited by noise and losses. Recently, Bozzio et al. (2018) have demonstrated experimentally how to replace challenging quantum verification with a classical channel and a quantum retrieval game (QRG). This brings QM significantly closer to practical realisation, but still thorough analysis of the revised scheme QM is required before it can be considered secure. We address this problem by presenting a proof-of-concept attack on QRG-based QM schemes, where we show that even imperfect quantum cloning can, under some circumstances, provide enough information to break a QRG-based QM scheme.

10.
Phys Rev Lett ; 122(17): 170501, 2019 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-31107073

RESUMO

We report an experimental implementation of tripartite controlled quantum teleportation on quantum optical devices. The protocol is performed through bi- and tripartite entangled channels of discrete variables and qubits encoded in the polarization of individual photons. The experimental results demonstrate successful controlled quantum teleportation with a fidelity around 83%, well above the classical limit. By realizing the controlled quantum teleportation through a biseparable state, we show that tripartite entanglement is not a necessary resource for controlled quantum teleportation, and the controller's capability to allow or prohibit the teleportation cannot be considered to be a manifestation of tripartite entanglement. These results open new possibilities for further application of controlled quantum teleportation by lowering the teleportation channel's requirements.

11.
Phys Rev Lett ; 123(26): 260501, 2019 Dec 31.
Artigo em Inglês | MEDLINE | ID: mdl-31951446

RESUMO

We report on the experimental measurement of the Hilbert-Schmidt distance between two two-qubit states by many-particle interference. We demonstrate that our three-step method for measuring distances in the Hilbert space is far less complex than reconstructing density matrices and that it can be applied in quantum-enhanced machine learning to reduce the complexity of calculating Euclidean distances between multidimensional points, which can be especially interesting for near term quantum technologies and quantum artificial intelligence research. Our results are also a novel example of applying mixed states in quantum information processing. Usually working with mixed states is undesired, but here it gives the possibility of encoding extra information as the degree of coherence between the given two dimensions of the density matrix.

12.
J Sep Sci ; 42(2): 556-565, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30411839

RESUMO

This work focused on the development and validation of the analytical procedure using gas chromatography equipped with vacuum-ultraviolet detection for the specific and sensitive determination of nine photoinitiators in food packages. Subsequently, a comparison of the combination of vacuum ultraviolet spectroscopy with gas chromatography and a developed gas chromatography with mass spectrometry method was performed. The vacuum-ultraviolet spectra of all tested photoinitiators were collected and found to be highly distinct, even for isomers. Under the optimal conditions, the limits of detection for nine photoinitiators ranged from 1 to 5 mg/L using vacuum ultraviolet detection and from 0.15 to 0.5 mg/L using mass spectrometric detection. Both techniques were successfully applied for screening of photoinitiators in seven kinds of food packages and the obtained data showed good agreement (the relative difference was between 3 and 18%). The variability in concentrations found in triplicate samples was assessed to be below 18%. Predominantly benzophenone was found in all analysed samples in the range of 0.31-4.23 mg/kg. It appears to be preferably selected by food packaging manufacturers. This study proposes a new simple and sensitive technique used for analysis of photoinitiators that could be a good alternative to gas chromatography with mass spectrometry.


Assuntos
Benzofenonas/análise , Contaminação de Alimentos/análise , Embalagem de Alimentos , Tinta , Fármacos Fotossensibilizantes/análise , Cromatografia Gasosa-Espectrometria de Massas , Espectrofotometria Ultravioleta , Vácuo
13.
Front Microbiol ; 9: 2356, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30349512

RESUMO

Background: Aspergillus fumigatus is a ubiquitous saprophytic airborne fungus responsible for more than one million deaths every year. The siderophores of A. fumigatus represent important virulence factors that contribute to the microbiome-metabolome dialog in a host. From a diagnostic point of view, the monitoring of Aspergillus secondary metabolites in urine of a host is promising due to the non-invasiveness, rapidity, sensitivity, and potential for standardization. Methods: Using a model of experimental aspergillosis in immunocompromised Lewis rats, the fungal siderophores ferricrocin (FC) and triacetylfusarinine C (TAFC) were monitored in rat urine before and after lung inoculation with A. fumigatus conidia. Molecular biomarkers in high-dose (HD) and low-dose (LD) infection models were separated using high performance liquid chromatography (HPLC) and were detected by mass spectrometry (MS). In the current work, we corroborated the in vivo MS infection kinetics data with micro-positron emission tomography/computed tomography (µPET/CT) kinetics utilizing 68Ga-labeled TAFC. Results: In the HD model, the initial FC signal reflecting aspergillosis appeared as early as 4 h post-infection. The results from seven biological replicates showed exponentially increasing metabolite profiles over time. In A. fumigatus, TAFC was found to be a less produced biomarker that exhibited a kinetic profile identical to that of FC. The amount of siderophores contributed by the inoculating conidia was negligible and undetectable in the HD and LD models, respectively. In the µPET/CT scans, the first detectable signal in HD model was recorded 48 h post-infection. Regarding the MS assay, among nine biological replicates in the LD model, three animals did not develop any infection, while one animal experienced an exponential increase of metabolites and died on day 6 post-infection. All remaining animals had constant or random FC levels and exhibited few or no symptoms to the experiment termination. In the LD model, the TAFC concentration was not statistically significant, while the µPET/CT scan was positive as early as 6 days post-infection. Conclusion: Siderophore detection in rat urine by MS represents an early and non-invasive tool for diagnosing aspergillosis caused by A. fumigatus. µPET/CT imaging further determines the infection location in vivo and allows the visualization of the infection progression over time.

14.
Sci Rep ; 8(1): 13480, 2018 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-30194419

RESUMO

For several decades, scientists have been aware of significant benefits allowing quantum information processing technologies to surpass their classical counterparts. Recent technological development allows these benefits to be tested experimentally and in some cases also implemented in practical devices. So far the majority of experimental quantum networks was limited to peer-to-peer communications between two parties. Practical implementation of quantum communications networks, however, needs to address the problem of scalability to serve large numbers of users. Similarly to classical computer networks, their quantum counterparts would require routing protocols to direct the signal from its source to destination. Devices implementing these routing protocols are called quantum routers and have recently been subject of an intense research. In this paper, we report on experimental implementation of a linear-optical quantum router. Our device allows single-photon polarization-encoded qubits to be routed coherently into two spatial output modes depending on the state of two identical control qubits. The polarization qubit state of the routed photon is maintained during the routing operation. The success probability of our scheme can be increased up to 25% making it the most efficient linear-optical quantum router developed to this date.

15.
Anal Chim Acta ; 1030: 25-32, 2018 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-30032770

RESUMO

A new laser ablation inductively coupled plasma mass spectrometry imaging (LA-ICP-MSI) method has been developed to visualize latent fingerprint of suspect persons possibly related to a criminal offence committed with a gun. Metallic impurities and metallic gunshot residues (GSRs) adhered on a latent fingerprint can link biometric information and shooting. The identification and spatial distribution of characteristic gunshot-related metals (Cu, Zn, Sb, Ba, Hg, Pb) was studied in detail. Observed limits of detection for the corresponding metals were below 0.3 ng cm-2. The distributions of the selected metals were simply transferred to images of fingerprints that can reveal a person somehow manipulating with a gun while the presence of characteristic and consistent GSR particles provided the evidence of the shooting. LA-ICP-MSI has been proved to be a unique tool in dactyloscopic identification of a suspect person from latent and commonly visualized fingerprints.


Assuntos
Dermatoglifia , Terapia a Laser , Metais/análise , Espectrometria de Massas
16.
Artigo em Inglês | MEDLINE | ID: mdl-29684910

RESUMO

Achievements of supercritical fluid chromatography with mass spectrometric detection made in the field of forensic science during the last decade are reviewed. The main topics include analysis of traditional drugs of abuse (e.g. cannabis, methamphetamine) as well as new psychoactive substances (synthetic cannabinoids, cathinones and phenethylamines), doping agents (anabolic steroids, stimulants, diuretics, analgesics etc.) and chemical warfare agents. Control of food authenticity, detection of adulteration and identification of toxic substances in food are also pointed out. Main aspects of an analytical workflow, such as sample preparation, separation and detection are discussed. A special attention is paid to the performance characteristics and validation parameters of supercritical fluid chromatography-mass spectrometric methods in comparison with other separation techniques.


Assuntos
Cromatografia com Fluido Supercrítico/métodos , Drogas Ilícitas/análise , Espectrometria de Massas/métodos , Animais , Doping nos Esportes , Análise de Alimentos , Humanos , Óleos Vegetais/química , Psicotrópicos/análise , Detecção do Abuso de Substâncias
17.
J Sep Sci ; 41(10): 2288-2295, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29461018

RESUMO

New psychoactive substances represent serious social and health problem as tens of new compounds are detected in Europe annually. They often show structural proximity or even isomerism, which complicates their analysis. Two methods based on ultra high performance supercritical fluid chromatography and ultra high performance liquid chromatography with mass spectrometric detection were validated and compared. A simple dilute-filter-and-shoot protocol utilizing propan-2-ol or methanol for supercritical fluid or liquid chromatography, respectively, was proposed to detect and quantify 15 cathinones and phenethylamines in human urine. Both methods offered fast separation (<3 min) and short total analysis time. Precision was well <15% with a few exceptions in liquid chromatography. Limits of detection in urine ranged from 0.01 to 2.3 ng/mL, except for cathinone (5 ng/mL) in supercritical fluid chromatography. Nevertheless, this technique distinguished all analytes including four pairs of isomers, while liquid chromatography was unable to resolve fluoromethcathinone regioisomers. Concerning matrix effects and recoveries, supercritical fluid chromatography produced more uniform results for different compounds and at different concentration levels. This work demonstrates the performance and reliability of supercritical fluid chromatography and corroborates its applicability as an alternative tool for analysis of new psychoactive substances in biological matrixes.


Assuntos
Cromatografia Líquida de Alta Pressão , Cromatografia com Fluido Supercrítico , Psicotrópicos/análise , Urinálise/métodos , Alcaloides , Calibragem , Humanos , Limite de Detecção , Espectrometria de Massas , Metanol/urina , Fenetilaminas/urina , Reprodutibilidade dos Testes , Solventes
18.
Anal Chim Acta ; 999: 60-68, 2018 Jan 25.
Artigo em Inglês | MEDLINE | ID: mdl-29254575

RESUMO

A carbon fiber brush electrode (CFBE) was newly designed and used as a substrate for both controlled potential electrolysis and atmospheric solids analysis probe (ASAP) mass spectrometry. Electropolymerized and strongly adsorbed products of electrolysis were directly desorbed and ionized from the electrode surface. Electrochemical properties of the electrode investigated by cyclic voltammetry revealed large electroactive surface area (23 ± 3 cm2) at 1.3 cm long array of carbon fibers with diameter 6-9 µm. Some products of electrochemical oxidation of pentabromophenol and 2,4,6-tribromophenol formed a compact layer on the carbon fibers and were analyzed using ASAP. Eleven new oligomeric products were identified including quinones and biphenoquinones. These compounds were not observed previously in electrolyzed solutions by liquid or gas chromatography/mass spectrometry. The thickness around 58 nm and 45 nm of the oxidation products layers deposited on carbon fibers during electrolysis of pentabromophenol and 2,4,6-tribromophenol, respectively, was estimated from atomic force microscopy analysis and confirmed by scanning electron microscopy with energy-dispersive X-ray spectroscopy measurements.

19.
Sci Rep ; 7(1): 16523, 2017 11 28.
Artigo em Inglês | MEDLINE | ID: mdl-29184111

RESUMO

Invasive pulmonary aspergillosis results in 450,000 deaths per year and complicates cancer chemotherapy, transplantations and the treatment of other immunosuppressed patients. Using a rat model of experimental aspergillosis, the fungal siderophores ferricrocin and triacetylfusarinine C were identified as markers of aspergillosis and quantified in urine, serum and lung tissues. Biomarkers were analyzed by matrix-assisted laser desorption ionization (MALDI) and electrospray ionization mass spectrometry using a 12T SolariX Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. The limits of detection of the ferri-forms of triacetylfusarinine C and ferricrocin in the rat serum were 0.28 and 0.36 ng/mL, respectively. In the rat urine the respective limits of detection achieved 0.02 and 0.03 ng/mL. In the sera of infected animals, triacetylfusarinine C was not detected but ferricrocin concentration fluctuated in the 3-32 ng/mL range. Notably, the mean concentrations of triacetylfusarinine C and ferricrocin in the rat urine were 0.37 and 0.63 µg/mL, respectively. The MALDI FTICR mass spectrometry imaging illustrated the actual microbial ferricrocin distribution in the lung tissues and resolved the false-positive results obtained by the light microscopy and histological staining. Ferricrocin and triacetylfusarinine C detection in urine represents an innovative non-invasive indication of Aspergillus infection in a host.


Assuntos
Aspergilose/diagnóstico , Aspergilose/microbiologia , Espectrometria de Massas , Animais , Aspergillus/química , Aspergillus/metabolismo , Biomarcadores , Cromatografia Líquida , Contagem de Colônia Microbiana , Modelos Animais de Doenças , Histocitoquímica , Humanos , Aspergilose Pulmonar Invasiva/diagnóstico , Aspergilose Pulmonar Invasiva/microbiologia , Pulmão/microbiologia , Pulmão/patologia , Espectrometria de Massas/métodos , Metabolômica/métodos , Ratos , Sideróforos/análise , Sideróforos/química , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodos
20.
Anal Chim Acta ; 989: 112-120, 2017 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-28915937

RESUMO

The ultra-high performance supercritical fluid chromatography-mass spectrometry (UHPSFC/MS) procedure for analysis of native monosaccharides was developed. Chromatographic conditions were investigated to separate a mixture of four hexoses, three pentoses, two deoxyhexoses and two uronic acids. Increasing water content in methanol modifier to 5% and formic acid to 4% improved peak shapes of neutral monosaccharides and allowed complete elution of highly polar uronic acids in a single run. An Acquity HSS C18SB column outperformed other three tested stationary phases (BEH (silica), BEH 2-ethylpyridine, CSH Fluoro-Phenyl) in terms of separation of isomers and analysis time (4.5 min). Limits of detection were in the range 0.01-0.12 ng µL-1. Owing to separation of anomers, identification of critical pairs (arabinose-xylose and glucose-galactose) was possible. Feasibility of the new method was demonstrated on plant-derived polysaccharide binders. Samples of watercolor paints, painted paper and three plant gums widely encountered in painting media (Arabic, cherry and tragacanth) were decomposed prior the analysis by microwave-assisted hydrolysis at 40 bar initial pressure using 2 mol L-1 trifluoroacetic acid. Among tested temperatures, 120 °C ensured appropriate hydrolysis efficiency for different types of gum and avoided excessive degradation of labile monosaccharides. Procedure recovery tested on gum Arabic was 101% with an RSD below 8%. Aqueous hydrolysates containing monosaccharides in different ratios specific to each type of plant gum were diluted or analyzed directly. Filtration of samples before hydrolysis reduced interferences from a paper support and identification of gum Arabic in watercolor-painted paper samples was demonstrated. Successful identification of pure gum Arabic was confirmed for sample quantities as little as 1 µg. Two classification approaches were compared and principal component analysis was superior to analysis based on peak area ratios of monosaccharides. The proposed procedure using UHPSFC/MS represents an interesting alternative which can compete with other chromatographic methods in the field of saccharide analysis in terms of speed, sensitivity and simplicity of workflow.


Assuntos
Cromatografia com Fluido Supercrítico , Monossacarídeos/análise , Gomas Vegetais/química , Pintura/análise , Papel , Polissacarídeos , Espectrometria de Massas em Tandem
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