RESUMO
BACKGROUND: Proton-transfer reaction time-of-flight mass spectrometry (PTR-TOF-MS) is a promising tool for a rapid online determination of exhaled volatile organic compounds (eVOCs) profiles in patients with cystic fibrosis (CF). OBJECTIVE: To detect VOC breath signatures specific to adult patients with CF compared with controls using PTR-TOF-MS. METHODS: 102 CF patients (54 M/48, mean age 25.6 ± 7.8 yrs) and 97 healthy controls (56 M/41F, mean age 25.8 ± 6.0 yrs) were examined. Samples from normal quiet breathing and forced expiratory maneuvers were analyzed with PTR-TOF-MS (Ionicon, Austria) to obtain VOC profiles listed as ions at various mass-to-charge ratios (m/z). RESULTS: PTR-TOF-MS analysis was able to detect 167 features in exhaled breath from CF patients and healthy controls. According to cluster analysis and LASSO regression, patients with CF and controls were separated. The most significant VOCs for CF were indole, phenol, dimethyl sulfide, and not indicated: m/z = 297.0720 ([C12H13N2O7 and C17H13O5]H + ), m/z = 281.0534 ([C19H7NO2, C12H11NO7 and C16H9O5]H + ) during five-fold cross-validation both in forced expiratory maneuver and in normal quiet breathing. CONCLUSION: PTR-TOF-MS is a promising method for determining the molecular composition of exhaled air specific to CF.
Assuntos
Testes Respiratórios , Fibrose Cística , Espectrometria de Massas , Compostos Orgânicos Voláteis , Humanos , Fibrose Cística/metabolismo , Fibrose Cística/diagnóstico , Testes Respiratórios/métodos , Adulto , Feminino , Compostos Orgânicos Voláteis/análise , Masculino , Expiração , Prótons , Adulto Jovem , Fatores de Tempo , Estudos de Casos e ControlesRESUMO
In this article, the specific features of competitive ionic and molecular transport in nanocomposite systems based on network membranes synthesized by radical polymerization of polyethylene glycol diacrylate in the presence of LiBF4, 1-ethyl-3-methylimidazolium tetrafluoroborate, ethylene carbonate (EC), and TiO2 nanopowder (d~21 nm) were studied for 1H, 7Li, 11B, 13C, and 19F nuclei using NMR. The membranes obtained were studied through electrochemical impedance, IR-Fourier spectroscopy, DSC, and TGA. The ionic conductivity of the membranes was up to 4.8 m Scm-1 at room temperature. The operating temperature range was from -40 to 100 °C. Two types of molecular and ionic transport (fast and slow) have been detected by pulsed field gradient NMR. From quantum chemical modeling, it follows that the difficulty of lithium transport is due to the strong chemisorption of BF4- anions with counterions on the surface of TiO2 nanoparticles. The theoretical conclusion about the need to increase the proportion of EC in order to reduce the influence of this effect was confirmed by an experimental study of a system with 4 moles of EC. It has been shown that this approach leads to an increase in lithium conductivity in an ionic liquid medium, which is important for the development of thermostable nanocomposite electrolytes for Li//LiFePO4 batteries with a base of lithium salts and aprotonic imidasolium ionic liquid.
RESUMO
The hydration of ions and charge groups controls electro mass transfer through ion exchange systems. The self-diffusion and local mobility of water molecules as well as lithium cations in poly (4-styrenesulfonic acid) and its lithium, sodium and cesium salts were investigated for the first time using pulsed-field gradient NMR (PFG NMR) and NMR relaxation techniques. The temperature dependences of the water molecule and Li+ cation self-diffusion coefficients exhibited increasing self-diffusion activation energy in temperature regions below 0 °C, which is not due to the freezing of parts of the water. The self-diffusion coefficients of water molecules and lithium cations, as measured using PFG NMR, are in good agreement with the self-diffusion coefficients calculated based on Einstein's equation using correlation times obtained from spin-lattice relaxation data. It was shown that macroscopic water molecules' and lithium cations' transfer is controlled by local particles jumping between neighboring sulfonated groups. These results are similar to the behavior of water and cations in sulfonic cation exchanger membranes and resins. It was concluded that polystyrenesulfonic acid is appropriate model of the ionogenic part of membranes based on this polymer.
RESUMO
Elementary processes of electro mass transfer in the nanocomposite polymer electrolyte system by pulse field gradient, spin echo NMR spectroscopy and the high-resolution NMR method together with electrochemical impedance spectroscopy are examined. The new nanocomposite polymer gel electrolytes consisted of polyethylene glycol diacrylate (PEGDA), salt LiBF4 and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) and SiO2 nanoparticles. Kinetics of the PEGDA matrix formation was studied by isothermal calorimetry. The flexible polymer-ionic liquid films were studied by IRFT spectroscopy, differential scanning calorimetry and temperature gravimetric analysis. The total conductivity in these systems was about 10-4 S cm-1 (-40 °C), 10-3 S cm-1 (25 °C) and 10-2 S cm-1 (100 °C). The method of quantum-chemical modeling of the interaction of SiO2 nanoparticles with ions showed the advantage of the mixed adsorption process, in which a negatively charged surface layer is formed from Li+ BF4- ions on silicon dioxide particles and then from ions of the ionic liquid EMI+ BF4-. These electrolytes are promising for use both in lithium power sources and in supercapacitors. The paper shows preliminary tests of a lithium cell with an organic electrode based on a pentaazapentacene derivative for 110 charge-discharge cycles.
RESUMO
The interconnection of ionogenic channel structure, cation hydration, water and ionic translational mobility was revealed in Nafion and MSC membranes based on polyethylene and grafted sulfonated polystyrene. A local mobility of Li+, Na+ and Cs+ cations and water molecules was estimated via the 1H, 7Li, 23Na and 133Cs spin relaxation technique. The calculated cation and water molecule self-diffusion coefficients were compared with experimental values measured using pulsed field gradient NMR. It was shown that macroscopic mass transfer is controlled by molecule and ion motion near sulfonate groups. Lithium and sodium cations whose hydrated energy is higher than water hydrogen bond energy move together with water molecules. Cesium cations in possession of low hydrated energy are directly jumping between neighboring sulfonate groups. Cation Li+, Na+ and Cs+ hydration numbers (h) in membranes were calculated from 1H chemical shift water molecule temperature dependences. The values calculated from the Nernst-Einstein equation and the experimental conductivity values were close to each other in Nafion membranes. In MSC membranes, calculated conductivities were one order of magnitude more compared to the experimental ones, which is explained by the heterogeneity of the membrane pore and channel system.
RESUMO
Fullerene derivatives are of great interest in various fields of science and technology. Fullerene derivatives are known to have pronounced anticancer and antiviral activity. They have antibacterial properties. Their properties are largely determined by association processes. Understanding the nature and properties of associates in solvents of various types will make it possible to make significant progress in understanding the mechanisms of aggregation of molecules of fullerene derivatives in solutions. Thus, this work, aimed at studying the size and stability of associates, is relevant and promising for further research. The NMR method in a pulsed field gradient was used, which makes it possible to directly study the translational mobility of molecules. The sizes of individual molecules and associates were calculated based on the Stokes-Einstein model. The lifetime of associates was also estimated. The interaction of water-soluble C60 fullerene derivatives with erythrocytes was also evaluated. The values of self-diffusion coefficients and the lifetime of molecules of their compounds in cell membranes are obtained. It is concluded that the molecules of fullerene derivatives are fixed on the cell surface, and their forward movement is controlled by lateral diffusion.
Assuntos
Fulerenos , Fulerenos/farmacologia , Fulerenos/química , Espectroscopia de Ressonância Magnética , Difusão , Água/química , EritrócitosRESUMO
The effect of the composition of liquid electrolytes in the bulk and at the interface with the LiFePO4 cathode on the operation of a solid-state lithium battery with a nanocomposite polymer gel electrolyte based on polyethylene glycol diacrylate and SiO2 was studied. The self-diffusion coefficients on the 7Li, 1H, and 19F nuclei in electrolytes based on LiBF4 and LiTFSI salts in solvents (gamma-butyrolactone, dioxolane, dimethoxyethane) were measured by nuclear magnetic resonance (NMR) with a magnetic field gradient. Four compositions of the complex electrolyte system were studied by high-resolution NMR. The experimentally obtained 1H chemical shifts are compared with those theoretically calculated by quantum chemical modeling. This made it possible to suggest the solvate shell compositions that facilitate the rapid transfer of the Li+ cation at the nanocomposite electrolyte/LiFePO4 interface and ensure the stable operation of a solid-state lithium battery.
RESUMO
NMR is the method of choice for molecular and ionic structures and dynamics investigations. The present review is devoted to solvation and mobilities in solid electrolytes, such as ion-exchange membranes and composite materials, based on cesium acid sulfates and phosphates. The applications of high-resolution NMR, solid-state NMR, NMR relaxation, and pulsed field gradient 1H, 7Li, 13C, 19F, 23Na, 31P, and 133Cs NMR techniques are discussed. The main attention is paid to the transport channel morphology, ionic hydration, charge group and mobile ion interaction, and translation ions and solvent mobilities in different spatial scales. Self-diffusion coefficients of protons and Li+, Na+, and Cs+ cations are compared with the ionic conductivity data. The microscopic ionic transfer mechanism is discussed.
Assuntos
Eletrólitos , Sódio , Cátions , Eletrólitos/química , Lítio/química , Espectroscopia de Ressonância Magnética , Prótons , Sódio/químicaRESUMO
This review is devoted to different types of novel polymer electrolytes for lithium power sources developed during the last decade. In the first part, the compositions and conductivity of various polymer electrolytes are considered. The second part contains NMR applications to the ion transport mechanism. Polymer electrolytes prevail over liquid electrolytes because of their exploitation safety and wider working temperature ranges. The gel electrolytes are mainly attractive. The systems based on polyethylene oxide, poly(vinylidene fluoride-co-hexafluoropropylene), poly(ethylene glycol) diacrylate, etc., modified by nanoparticle (TiO2, SiO2, etc.) additives and ionic liquids are considered in detail. NMR techniques such as high-resolution NMR, solid-state NMR, magic angle spinning (MAS) NMR, NMR relaxation, and pulsed-field gradient NMR applications are discussed. 1H, 7Li, and 19F NMR methods applied to polymer electrolytes are considered. Primary attention is given to the revelation of the ion transport mechanism. A nanochannel structure, compositions of ion complexes, and mobilities of cations and anions studied by NMR, quantum-chemical, and ionic conductivity methods are discussed.
RESUMO
Here we report a reaction of the fullerene derivatives C60Ar5Cl, which enables the substitution of Cl with thiophene residues and the formation of the novel family of C1-symmetrical C60 fullerene derivatives with six functional addends C60Ar5Th. The discovered reaction provided a straightforward approach to the synthesis of previously inaccessible multifunctional water-soluble fullerene derivatives, including the compounds with antiviral activity against human immunodeficiency and influenza viruses.
Assuntos
Antivirais/química , Fulerenos/química , Tiofenos/química , Antivirais/farmacologia , Humanos , Estrutura Molecular , Água/químicaRESUMO
The results of NMR, and especially pulsed field gradient NMR (PFG NMR) investigations, are summarized. Pulsed field gradient NMR technique makes it possible to investigate directly the partial self-diffusion processes in spatial scales from tenth micron to millimeters. Modern NMR spectrometer diffusive units enable to measure self-diffusion coefficients from 10-13 m2/s to 10-8 m2/s in different materials on 1 H, 2 H, 7 Li, 13 C, 19 F, 23 Na, 31 P, 133 Cs nuclei. PFG NMR became the method of choice for reveals of transport mechanism in polymeric electrolytes for lithium batteries and fuel cells. Second wide field of application this technique is the exchange processes and lateral diffusion in biological cells as well as molecular association of proteins. In this case a permeability, cell size, and associate lifetime could be estimated. The authors have presented the review of their research carried out in Karpov Institute of Physical Chemistry, Moscow, Russia; Institute of Problems of Chemical Physics RAS, Chernogolovka, Russia; Kazan Federal University, Kazan, Russia; Korea University, Seoul, South Korea; Yokohama National University, Yokohama, Japan. The results of water molecule and Li+, Na+, Cs+ cation self-diffusion in Nafion membranes and membranes based on sulfonated polystyrene, water (and water soluble) fullerene derivative permeability in RBC, casein molecule association have being discussed.
RESUMO
Cystic fibrosis (CF) is the most common monogenic autosomal recessive disease, associated with pathogenic variants in the CFTR gene. The splicing variant c.3140-16T>A (3272-16T>A) has been described previously and, according to the Russian CF Patients Registry, occurs with a frequency of 0.34%. The phenotypic features of CF patients with the c.3140-16T>A variant were compared with those of patients with the genotype F508del/F508del. Patients with the allele c.3140-16T>A had higher average age and age at diagnosis, and the allele was present in a greater proportion of adults. Patients carrying the c.3140-16T>A allele were characterised by better physical development indicators, both in adults and in children, had preserved pancreatic function, as well as the absence of a number of complications, and required pancreatic enzyme replacement therapy less often than patients with the F508del/F508del genotype. Sweat test values also were lower in patients with the c.3140-16T>A genotype. According to the results of clinical and laboratory studies, the phenotype of patients with the genetic variant c.3140-16T>A can be considered "mild". Functional CFTR protein activity in the presence of c.3140-16T>A was evaluated using intestinal current measurements (ICM) and the forskolin-induced swelling assay on organoids obtained from patients' rectal biopsies. c.3140-16T>A had high residual CFTR channel activity and was amenable to effective pharmacological correction with thea VX-770 potentiator. To evaluate the effect of the variant on CFTR pre-mRNA splicing we performed a minigene assay, as well as RT-PCR analysis of RNA isolated from the nasal epithelium and rectal biopsy of patients. We showed that the c.3140-16T>A variant creates a novel acceptor AG dinucleotide within CFTR intron 19, resulting in a 14-nucleotide extension of exon 20. This frameshift produces a premature termination codon and triggers mRNA degradation by the nonsense-mediated decay (NMD) mechanism. Moreover, we observed that the c.3140-16T>A allele could produce a residual amount of normally spliced transcript, thus explaining the patient's mild phenotype.
Assuntos
Regulador de Condutância Transmembrana em Fibrose Cística/genética , Fibrose Cística/genética , Genótipo , Fenótipo , Adolescente , Adulto , Células Cultivadas , Criança , Fibrose Cística/metabolismo , Fibrose Cística/patologia , Regulador de Condutância Transmembrana em Fibrose Cística/metabolismo , Feminino , Mutação da Fase de Leitura , Humanos , Masculino , Mucosa Nasal/metabolismo , Degradação do RNAm Mediada por Códon sem Sentido , Organoides/metabolismo , Suor/metabolismoRESUMO
Cyclic oxoammonium salts and DMSO are known as important reagents for their diverse and unique reactivity. In the present work, we have studied the reaction of six- and five-membered oxoammonium salts with DMSO. The reaction includes â¼100% selective transfer of the O atom from the >N+âO group to the S atom of DMSO and structural rearrangement of the remaining cationic framework, leading to the formation of hydrolytically unstable iminium salts. The logarithms of the bimolecular rate constants k of the reaction correlated linearly with the reduction potentials E>N+âO/>N-Oâ¢, a relationship known for other electrophile-nucleophile combinations. The kinetic data and results of the DFT calculations allow for the suggestion that the studied process proceeds via the prereactive charge-transfer complex >N+âO···S (O)Me2 and its direct concerted rearrangement to the iminium salts. An alternative mechanism that includes intermediate steps with discrete nitrenium cations can be ruled out on the basis of product analysis and DFT computations. The obtained results allow a deeper understanding of the redox chemistry of a pair of nitroxide radicals-oxoammonium cations.
RESUMO
The main particularities of sulfonate groups hydration, water molecule, and alkaline metal cation translation mobility were revealed by nuclear magnetic resonance (NMR) and ionic conductivity measurements techniques in cation-exchange membranes MSC based on cross-linked sulfonated polystyrene (PS) grafted on polyethylene with ion-exchange capacity of 2.5 mg-eq/g. Alkaline metal cation hydration numbers (h) calculated from temperature dependences of 1H chemical shift of water molecule for membranes equilibrated with water vapor at RH = 95% are 5, 6, and 4 for Li+, Na+, and Cs+ ions, respectively. These values are close to h for equimolar aqueous salt solutions. Water molecules and counter ions Li+, Na+, and Cs+ diffusion coefficients were measured by pulsed field gradient NMR on the 1H, 7Li, 23Na, and 133Cs nuclei. For membranes as well as for aqueous chloride solutions, cation diffusion coefficients increased in the following sequence: Li+ < Na+ < Cs+. Cation and water molecule diffusion activation energies in temperature range from 20 °C to 80 °C were close to each other (about 20 kJ/mol). The cation conductivity of MSC membranes is in the same sequence, Li+ < Na+ < Cs+ << H+. The conductivity values calculated from the NMR diffusion coefficients with the use of the Nernst-Einstein equation are essentially higher than experimentally determined coefficients. The reason for this discrepancy is the heterogeneity of membrane pore and channel system. Ionic conductivity is limited by cation transfer in narrow channels, whereas the diffusion coefficient characterizes ion mobility in wide pores first of all.
RESUMO
Recently developed non-functional derivatives of polymethylsilsesquioxane (PMSSO) dendrimers of the first to fifth generation were characterized by 1H, 13C and 29Si NMR spectroscopy. The self-diffusion and NMR relaxation of PMSSO dendrimers in dilute solutions of toluene and melts were investigated in a wide temperature range (-50-80 °C). The hydrodynamic radii of dendrimers were determined from the self-diffusion coefficients measured in diluted solutions according to the Stokes-Einstein equation. The hydrodynamic radius of PMSSO dendrimers as a function of molecular mass follows a power law with the scaling exponent of 0.32 ± 0.02 in the investigated temperature range. The temperature dependences of the self-diffusion coefficients of dendrimers were described by the Arrhenius-type equation. The activation energies of self-diffusion of dendrimers in diluted toluene solutions are identical for different generations while the dependence of activation energy for dendrimers in melts shows a maximum for the third generation (G3) dendrimer. Taking into account the absence of specific interactions in PMSSO dendrimer melts the observed behavior was ascribed to the manifestation of interpenetration of dendrimer molecules. For low generations (G1 and G2) the short length of the branches does not considerably affect the translational diffusion while for higher generations (G4 and G5) the densification of the structure prevents significant interpenetration.
RESUMO
We have synthesized a series of water-soluble polycarboxylic derivatives of [60]fullerene with a gradually changed polarity by combining three to five polar (ionic) malonate addends with two to zero hydrophobic dichlorobenzene units and explored their antiviral activity. It has been shown that decreasing the number of the ionogenic carboxylic groups in the molecules enhanced their antiviral activity against HIV-1 and suppressed their action against HIV-2. The obtained results implied that the charged states and hydrophobicity of the water-soluble polycarboxylic fullerene derivatives affect significantly their biological properties.
Assuntos
Fármacos Anti-HIV/farmacologia , Ácidos Carboxílicos/farmacologia , Clorobenzenos/química , Fulerenos/química , HIV-1/efeitos dos fármacos , HIV-2/efeitos dos fármacos , Polímeros/farmacologia , Fármacos Anti-HIV/síntese química , Fármacos Anti-HIV/química , Ácidos Carboxílicos/síntese química , Ácidos Carboxílicos/química , Células Cultivadas , Humanos , Interações Hidrofóbicas e Hidrofílicas , Testes de Sensibilidade Microbiana , Estrutura Molecular , Polímeros/síntese química , Polímeros/química , Solubilidade , Água/químicaRESUMO
13 C and 15 N NMR spectra of high-energy 2,4,6-triazidopyridine-3,5-dicarbonitrile, 2,3,5,6-tetraazidopyridine-4-carbonitrile and 3,4,5,6-tetraazidopyridine-2-carbonitrile are reported. The assignment of signals in the spectra was performed on the basis of density functional theory calculations. The molecular geometries were optimized using the M06-2X functional with the 6-311+G(d,p) basis set. The magnetic shielding tensors were calculated by the gauge-independent atomic orbital method with the Tao-Perdew-Staroverov-Scuseria hybrid functional known as TPSSh. In all the calculations, a polarizable continuum model was used to simulate solvent effects. This approach provided accurate predictions of the 13 C and 15 N chemical shifts for all the three compounds despite complications arising due to non-coplanar arrangement of the azido groups in the molecules. It was found that the 15 N chemical shifts of the Nα atoms in the azido groups of 2,4,6-triazidopyridines correlate with the 13 C chemical shifts of the carbon atoms attached to these azido groups. Copyright © 2016 John Wiley & Sons, Ltd.
RESUMO
We report novel synthetic routes for facile preparation of highly functionalized fullerene derivatives C60(OR)5X (X = H, Cl, Br), C60(OR)4O and C60(OR)2 from chlorofullerene C60Cl6. The first water-soluble fullerene compound bearing residues of 3-oxypropanoic acid demonstrated a potent anti-HIV activity.
RESUMO
2,4,6-Triazido-s-triazine, 2,4,6-triazidopyrimidine and six different 2,4,6-triazidopyridines were studied by (15)N NMR spectroscopy. The assignment of signals in the spectra was performed using the gauge-independent atomic orbital (GIAO)-Tao-Perdew-Staroverov-Scuseria exchange-correlation functional (TPSS)h/6-311+G(d,p) calculations on the M06-2X/6-311+G(d,p) optimized molecular geometries. The Truhlar and coworkers' continuum solvation model called SMD was applied to treat solvent effects. With this approach, the root mean square error in estimations of the (15)N chemical shifts for the azido groups was just 1.9 ppm. It was shown that the different reactivity of the α- and γ-azido groups in pyridines correlates well with the chemical shifts of the Nα signals of these groups. Of two nonequivalent azido groups of azines, the azido group with the most shielded Nα signal is the most electron-deficient and reactive toward electron-rich reagents. By contrast, the azido group of azines with the most deshielded Nα signal is the most reactive toward electron-poor reagents.
Assuntos
Azidas/química , Pirimidinas/química , Triazinas/química , Espectroscopia de Ressonância Magnética/normas , Estrutura Molecular , Isótopos de Nitrogênio , Padrões de ReferênciaRESUMO
We report Arbuzov-type reactions of chlorofullerene C(60)Cl(6) with trialkyl phosphites producing highly functionalized fullerene derivatives C(60)[P(O)(OR)(2)](5)H with high yields. The designed family of [60]fullerene phosphonic acids and their esters showed unusual properties which might find valuable material science applications.