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1.
Phys Chem Chem Phys ; 26(20): 14970-14979, 2024 May 22.
Artículo en Inglés | MEDLINE | ID: mdl-38739372

RESUMEN

Curcumin is a medicinal agent that exhibits anti-cancer and anti-Alzheimer's disease properties. It has a keto-enol moiety that gives rise to many of its chemical properties including metal complexation and acid-base equilibria. A previous study has shown that keto-enol tautomerization at this moiety is implicated in the anti-Alzheimer's disease effect of curcumin, highlighting the importance of this process. In this study, tautomerization of curcumin in methanol, acetone and acetonitrile was investigated using time-resolved 1H nuclear magnetic resonance spectroscopy. Curcumin undergoes hydrogen-deuterium exchange with the solvents and the proton resonance peak corresponding to the hydrogen at the α-carbon position (Cα) decays as a function of time, signifying deuteration at this position. Because tautomerization is the rate limiting step in the deuteration of curcumin at the Cα position, the rate of tautomerization is inferred from the rate of deuteration. The rate constant of tautomerization of curcumin shows a temperature dependence and analysis using the Arrhenius equation revealed activation energies (Ea) of tautomerization of (80.1 ± 5.9), (64.1 ± 1.0) and (68.3 ± 5.5) kJ mol-1 in methanol, D2O/acetone and D2O/acetonitrile, respectively. Insight into the role of water in tautomerization of curcumin was further offered by density functional theory studies. The transition state of tautomerization was optimized in the presence of water molecules. The results show a hydrogen-bonded solvent bridge between the diketo moiety and Cα of curcumin. The Ea of tautomerization of curcumin shows a strong dependence on the number of water molecules in the solvent bridge, indicating the critical role played by the solvent bridge in catalyzing tautomerization of curcumin.


Asunto(s)
Curcumina , Curcumina/química , Metanol/química , Acetonitrilos/química , Acetona/química , Isomerismo , Termodinámica , Solventes/química
2.
J Chromatogr A ; 1722: 464856, 2024 May 10.
Artículo en Inglés | MEDLINE | ID: mdl-38579610

RESUMEN

Complex mixture analysis requires high-efficiency chromatography columns. Although reversed phase liquid chromatography (RPLC) is the dominant approach for such mixtures, hydrophilic interaction liquid chromatography (HILIC) is an important complement to RPLC by enabling the separation of polar compounds. Chromatography theory predicts that small particles and long columns will yield high efficiency; however, little work has been done to prepare HILIC columns longer than 25 cm packed with sub-2 µm particles. In this work, we tested the slurry packing of 75 cm long HILIC columns with 1.7 µm bridged-ethyl-hybrid amide HILIC particles at 2,100 bar (30,000 PSI). Acetonitrile, methanol, acetone, and water were tested as slurry solvents, with acetonitrile providing the best columns. Slurry concentrations of 50-200 mg/mL were assessed, and while 50-150 mg/mL provided comparable results, the 150 mg/mL columns provided the shortest packing times (9 min). Columns prepared using 150 mg/mL slurries in acetonitrile yielded a reduced minimum plate height (hmin) of 3.3 and an efficiency of 120,000 theoretical plates for acenaphthene, an unretained solute. Para-toluenesulfonic acid produced the lowest hmin of 1.9 and the highest efficiency of 210,000 theoretical plates. These results identify conditions for producing high-efficiency HILIC columns with potential applications to complex mixture analysis.


Asunto(s)
Acetonitrilos , Bencenosulfonatos , Interacciones Hidrofóbicas e Hidrofílicas , Acetonitrilos/química , Cromatografía Liquida/métodos , Cromatografía de Fase Inversa/métodos , Cromatografía de Fase Inversa/instrumentación , Metanol/química , Solventes/química , Acetona/química , Tamaño de la Partícula , Presión , Agua/química
3.
ACS Sens ; 9(4): 2183-2193, 2024 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-38588327

RESUMEN

Sensitive and selective acetone detection is of great significance in the fields of environmental protection, industrial production, and individual health monitoring from exhaled breath. To achieve this goal, bimetallic Au@Pt core-shell nanospheres (BNSs) functionalized-electrospun ZnFe2O4 nanofibers (ZFO NFs) are prepared in this work. Compared to pure NFs-650 analogue, the ZFO NFs/BNSs-2 sensor exhibits a stronger mean response (3.32 vs 1.84), quicker response/recovery speeds (33 s/28 s vs 54 s/42 s), and lower operating temperature (188 vs 273 °C) toward 0.5 ppm acetone. Note that an experimental detection limit of 30 ppb is achieved, which ranks among the best cases reported thus far. Besides the demonstrated excellent repeatability, humidity-enhanced response, and long-term stability, the selectivity toward acetone is remarkably improved after BNSs functionalization. Through material characterizations and DFT calculations, all these improvements could be attributed to the boosted oxygen vacancies and abundant Schottky junctions between ZFO NFs and BNSs, and the synergistic catalytic effect of BNSs. This work offers an alternative strategy to realize selective subppm acetone under high-humidity conditions catering for the future requirements of noninvasive breath diabetes diagnosis in the field of individual healthcare.


Asunto(s)
Acetona , Pruebas Respiratorias , Oro , Nanofibras , Nanosferas , Platino (Metal) , Acetona/análisis , Acetona/química , Nanofibras/química , Oro/química , Pruebas Respiratorias/métodos , Nanosferas/química , Platino (Metal)/química , Humanos , Límite de Detección , Oxígeno/química , Técnicas Electroquímicas/métodos
4.
J Chromatogr A ; 1724: 464898, 2024 Jun 07.
Artículo en Inglés | MEDLINE | ID: mdl-38669941

RESUMEN

The present research work was dedicated to developing an efficient method based on liquid-liquid chromatography (centrifugal partition chromatography, CPC) applicable to routine purifications of ochratoxins (OT) from the liquid culture of the strain A. albertensis SZMC 2107. The crude extract contained numerous components in addition to OTA (90.1 %,) and OTB (1.1 %,) according to HPLC examinations. For the separation of OTs by CPC, several tertiary systems based on acetonitrile, acetone, and short-chain alcohols were examined to find the most applicable biphasic system. The hexane/i-propanol/water 35:15:50 system supplemented with 0.1 % acetic acid was found to be the most efficient for use in CPC separation. Using liquid-liquid instrumental separation, the two OTs, namely OTA (2.23 mg) and OTB (0.031 mg), were successfully isolated with 96.3 % and-72.8 % purity, respectively, from 1 L ferment broth. The identities and purities of the purified components were confirmed and the performance parameters of each separation step and the whole procedure were determined. The developed method could be used effectively to purify OTs for analytical or toxicological applications.


Asunto(s)
Ocratoxinas , Ocratoxinas/análisis , Ocratoxinas/aislamiento & purificación , Ocratoxinas/química , Cromatografía Líquida de Alta Presión/métodos , Centrifugación/métodos , Cromatografía Liquida/métodos , Acetonitrilos/química , Acetona/química
5.
J UOEH ; 46(1): 9-16, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38479880

RESUMEN

This study investigated the permeation resistance of chemical protective gloves made of laminate film comprising nylon, ethylene-vinyl alcohol copolymer (EVOH), and other materials against different chemical substances to examine their usability in different work processes. The permeation resistance of the chemical protective glove was tested using the Japanese Industrial Standards (JIS) test method against twelve substances: acetone, acetonitrile, dichloromethane, ethyl acetate, n-hexane, methanol, tetrahydrofuran, toluene, 2-propanol, 1-butanol, 1,4-diethylene dioxide, and ethanol. After 480 min, no substance, except for methanol and ethanol, permeated at a standard permeation rate of 0.1 µg/cm2/min. Methanol and ethanol showed permeation at 1 min and 30 min elapsed, respectively. Hence, the gloves tested in this study exhibited permeation resistance to various chemical substances, and can thus be used in many work processes. Some film materials have short permeation time against certain chemical substances, but the chemical protective gloves tested in this study can be used at work sites, such as manufacturing sites, that require permeation resistance to different chemical substances.


Asunto(s)
Guantes Protectores , Exposición Profesional , Metanol , Etanol/química , Acetona/química , Tolueno/química
6.
Magn Reson Med ; 92(1): 215-225, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38321594

RESUMEN

PURPOSE: Determine the correct mathematical phase description for balanced steady-state free precession (bSSFP) signals in multi-compartment systems. THEORY AND METHODS: Based on published bSSFP signal models, different phase descriptions can be formulated: one predicting the presence and the other predicting the absence of destructive interference effects in multi-compartment systems. Numerical simulations of bSSFP signals of water and acetone were performed to evaluate the predictions of these different phase descriptions. For experimental validation, bSSFP profiles were measured at 3T using phase-cycled bSSFP acquisitions performed in a phantom containing mixtures of water and acetone, which replicates a system with two signal components. Localized single voxel MRS was performed at 7T to determine the relative chemical shift of the acetone-water mixtures. RESULTS: Based on the choice of phase description, the simulated bSSFP profiles of water-acetone mixtures varied significantly, either displaying or lacking destructive interference effects, as predicted theoretically. In phantom experiments, destructive interference was consistently observed in the measured bSSFP profiles of water-acetone mixtures, supporting the theoretical description that predicts such interference effects. The connection between the choice of phase description and predicted observation enables unambiguous experimental identification of the correct phase description for multi-compartment bSSFP profiles, which is consistent with the Bloch equations. CONCLUSION: The study emphasizes that consistent phase descriptions are crucial for accurately describing multi-compartment bSSFP signals, as incorrect phase descriptions result in erroneous predictions.


Asunto(s)
Acetona , Algoritmos , Simulación por Computador , Imagen por Resonancia Magnética , Fantasmas de Imagen , Agua , Imagen por Resonancia Magnética/métodos , Agua/química , Acetona/química , Acetona/análisis , Humanos , Procesamiento de Imagen Asistido por Computador/métodos , Reproducibilidad de los Resultados , Procesamiento de Señales Asistido por Computador
7.
Soft Matter ; 20(3): 495-510, 2024 Jan 17.
Artículo en Inglés | MEDLINE | ID: mdl-38088053

RESUMEN

Jellyfish as a potential sustainable food material has recently gained increasing interest. However, with their soft gel-like texture and easy spoilage, it remains challenging to achieve desirable edible structures from jellyfish. The culinary preparation of jellyfish is a complex process and extends beyond conventional cooking methods. In this study, we investigate the transformation of jellyfish into crispy-like structures by manipulating their microstructural and mechanical properties through a solvent-based preparation. The study focuses on the use of "poor solvents", namely ethanol and acetone, and employs rheology measurements and quantitative microscopy techniques to analyze the effects of these solvents on the mechanical properties and microstructure of jellyfish. Our findings reveal that both ethanol and acetone lead to a significant increase in jellyfish hardness and deswelling. Notably, a micro-scale network is formed within the jellyfish matrix, and this network is then mechanically reinforced before a crispy-like texture can be obtained. Our study points to solvent polarity as also being a crucial factor for creating these effects and determines an upper polarity limit in the range of 12.2-12.9 MPa1/2 for added solvents, corresponding to approximately 60% of added ethanol or 70% of added acetone. Our study highlights that solvent-based preparation serves as a "reverse cooking" technique, where mechanical modification rather than traditional softening mechanisms are employed to stabilize and strengthen the microstructures and fibers of jellyfish. By elucidating the underlying mechanisms of solvent-induced stabilization, our findings may facilitate the development of innovative and sustainable culinary practices, paving the way for broader applications of jellyfish and other soft edible materials in the gastronomic landscape.


Asunto(s)
Acetona , Etanol , Solventes/química , Acetona/química , Etanol/química
8.
Nature ; 626(7999): 542-548, 2024 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-38109940

RESUMEN

The success of colloidal semiconductor nanocrystals (NCs) in science and optoelectronics is inextricable from their surfaces. The functionalization of lead halide perovskite NCs1-5 poses a formidable challenge because of their structural lability, unlike the well-established covalent ligand capping of conventional semiconductor NCs6,7. We posited that the vast and facile molecular engineering of phospholipids as zwitterionic surfactants can deliver highly customized surface chemistries for metal halide NCs. Molecular dynamics simulations implied that ligand-NC surface affinity is primarily governed by the structure of the zwitterionic head group, particularly by the geometric fitness of the anionic and cationic moieties into the surface lattice sites, as corroborated by the nuclear magnetic resonance and Fourier-transform infrared spectroscopy data. Lattice-matched primary-ammonium phospholipids enhance the structural and colloidal integrity of hybrid organic-inorganic lead halide perovskites (FAPbBr3 and MAPbBr3 (FA, formamidinium; MA, methylammonium)) and lead-free metal halide NCs. The molecular structure of the organic ligand tail governs the long-term colloidal stability and compatibility with solvents of diverse polarity, from hydrocarbons to acetone and alcohols. These NCs exhibit photoluminescence quantum yield of more than 96% in solution and solids and minimal photoluminescence intermittency at the single particle level with an average ON fraction as high as 94%, as well as bright and high-purity (about 95%) single-photon emission.


Asunto(s)
Diseño de Fármacos , Ligandos , Nanopartículas del Metal , Puntos Cuánticos , Acetona/química , Alcoholes/química , Aniones , Compuestos de Calcio/química , Cationes , Coloides/química , Plomo , Mediciones Luminiscentes , Espectroscopía de Resonancia Magnética , Nanopartículas del Metal/química , Simulación de Dinámica Molecular , Óxidos/química , Fosfolípidos/química , Puntos Cuánticos/química , Solventes/química , Espectroscopía Infrarroja por Transformada de Fourier , Titanio/química
9.
PLoS One ; 18(7): e0288102, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-37418444

RESUMEN

Plate-based proteomic sample preparation offers a solution to the large sample throughput demands in the biotechnology field where hundreds or thousands of engineered microbes are constructed for testing is routine. Meanwhile, sample preparation methods that work efficiently on broader microbial groups are desirable for new applications of proteomics in other fields, such as microbial communities. Here, we detail a step-by-step protocol that consists of cell lysis in an alkaline chemical buffer (NaOH/SDS) followed by protein precipitation with high-ionic strength acetone in 96-well format. The protocol works for a broad range of microbes (e.g., Gram-negative bacteria, Gram-positive bacteria, non-filamentous fungi) and the resulting proteins are ready for tryptic digestion for bottom-up quantitative proteomic analysis without the need for desalting column cleanup. The yield of protein using this protocol increases linearly with respect to the amount of starting biomass from 0.5-2.0 OD*mL of cells. By using a bench-top automated liquid dispenser, a cost-effective and environmentally-friendly option to eliminating pipette tips and reducing reagent waste, the protocol takes approximately 30 minutes to extract protein from 96 samples. Tests on mock mixtures showed expected results that the biomass composition structure is in close agreement with the experimental design. Lastly, we applied the protocol for the composition analysis of a synthetic community of environmental isolates grown on two different media. This protocol has been developed to facilitate rapid, low-variance sample preparation of hundreds of samples and allow flexibility for future protocol development.


Asunto(s)
Acetona , Proteómica , Acetona/química , Proteómica/métodos , Proteínas , Indicadores y Reactivos
10.
Bioresour Technol ; 382: 129175, 2023 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-37187333

RESUMEN

This work demonstrated that bio-jet fuels can be directionally prepared from bagasse (a typical lignocellulose biomass) by integrating bio- and chemical catalysis reaction processes. This controllable transformation started with the preparation of acetone/butanol/ethanol (ABE) intermediates through the enzymolysis and fermentation of bagasse. Pretreatment of bagasse by deep eutectic solvent (DES) promoted the enzymatic hydrolysis and fermentation because it destroyed the structure of biomass and remove lignin in lignocellulose. Subsequently, the selective catalytic conversion of sugarcane derived ABE broth to jet range fuels was achieved through an integrated process: ABE dehydration to light olefins over the HSAPO-34 catalyst and olefin polymerization to bio-jet fuels over the Ni/HBET catalyst. The dual catalyst bed synthesis mode improved the selectively of bio-jet fuels. High selectivity of jet range fuels (83.0 %) and high conversion of ABE (95.3 %) were obtained by the integrated process.


Asunto(s)
Acetona , Alquenos , Fermentación , Acetona/química , Polimerizacion , Biomasa , Etanol/química , Butanoles , 1-Butanol
11.
Environ Res ; 229: 115931, 2023 07 15.
Artículo en Inglés | MEDLINE | ID: mdl-37076034

RESUMEN

A nano-enabled low-trace monitoring system for acetone has the potential to revolutionize breath omics-based non-invasive diagnosis of human diabetes and environmental monitoring technologies. This unprecedented study presents the state-of-the-art facile and economic template-assisted hydrothermal route to fabricate novel CuMoO4 nanorods for room temperature breath and airborne acetone detection. Physicochemical attribute analysis reveals the formation of crystalline CuMoO4 nanorods with diameters ranging from 90 to 150 nm, and an optical band gap of approximately 3.87 eV. CuMoO4 nanorods-based chemiresistor demonstrates excellent acetone monitoring performance, with a sensitivity of approximately 33.85 at a concentration of 125 ppm. Acetone detection is rapid, with a response time of 23 s and fast recovery within 31 s. Furthermore, the chemiresistor exhibits long-term stability and selectivity towards acetone, compared to other interfering volatile organic compounds (VOCs) commonly found in human breath such as ethanol, propanol, formaldehyde, humidity, and ammonia. The linear detection range of acetone from 25 to 125 ppm achieved by the fabricated sensor is well-suited for human breath-based diagnosis of diabetes. This work represents a significant advancement in the field, as it offers a promising alternative to time-consuming and costly invasive biomedical diagnostics, with the potential for application in cleanroom facilities for indoor contamination monitoring. The utilization of CuMoO4 nanorods as sensing nanoplatform opens new possibilities for the development of nano-enabled, low-trace acetone monitoring technologies for non-invasive diabetes diagnosis and environmental sensing applications.


Asunto(s)
Diabetes Mellitus , Nanotubos , Compuestos Orgánicos Volátiles , Humanos , Acetona/análisis , Acetona/química , Pruebas Respiratorias , Diabetes Mellitus/diagnóstico , Compuestos Orgánicos Volátiles/análisis
12.
Molecules ; 28(3)2023 Jan 24.
Artículo en Inglés | MEDLINE | ID: mdl-36770820

RESUMEN

Metal oxide (MOx) gas sensors have attracted considerable attention from both scientific and practical standpoints. Due to their promising characteristics for detecting toxic gases and volatile organic compounds (VOCs) compared with conventional techniques, these devices are expected to play a key role in home and public security, environmental monitoring, chemical quality control, and medicine in the near future. VOCs (e.g., acetone) are blood-borne and found in exhaled human breath as a result of certain diseases or metabolic disorders. Their measurement is considered a promising tool for noninvasive medical diagnosis, for example in diabetic patients. The conventional method for the detection of acetone vapors as a potential biomarker is based on spectrometry. However, the development of MOx-type sensors has made them increasingly attractive from a medical point of view. The objectives of this review are to assess the state of the art of the main MOx-type sensors in the detection of acetone vapors to propose future perspectives and directions that should be carried out to implement this type of sensor in the field of medicine.


Asunto(s)
Diabetes Mellitus , Compuestos Orgánicos Volátiles , Humanos , Acetona/química , Gases/análisis , Óxidos/química , Diabetes Mellitus/diagnóstico , Compuestos Orgánicos Volátiles/análisis
13.
Int J Biol Macromol ; 225: 1449-1461, 2023 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-36436598

RESUMEN

One of the key strategies for valorizing kraft lignin (KL) into value-added products such as bio-based adhesives is to perform solvent fractionation of KL to produce lignin with improved homogeneity. Understanding the structure and properties of fractionated KL will aid in the selection of the best samples for certain applications. In this study, acetone-fractionated KL from softwood and hardwood was characterized to understand its chemical structure, elemental composition, molecular weight, and thermal properties. The results revealed that acetone-insoluble KL (AIKL) fractions from softwood and hardwood have greater molecular weight, polydispersity, glass temperature, carbohydrate content, aliphatic hydroxyl groups, and a variety of native wood lignin side chains. In contrast, acetone-soluble KL (ASKL) fractions have a significantly lower molecular weight and polydispersity, a lower glass-transition temperature, a more condensed structure, more aromatic hydroxyl groups, and fewer native wood lignin side chains. In addition, the ASKL samples demonstrated stronger adhesive force and work of adhesion toward phenol-formaldehyde (PF) and urea-formaldehyde (UF) resins than the AIKL samples, regardless of the lignin source. These findings suggest that ASKL has great potential as a substitute for phenol in PF resins and as a green additive to reinforce UF resins.


Asunto(s)
Acetona , Lignina , Lignina/química , Acetona/química , Estructura Molecular , Fenoles , Fenol/química , Formaldehído/química , Adhesivos/química
14.
Anal Methods ; 14(44): 4514-4522, 2022 11 18.
Artículo en Inglés | MEDLINE | ID: mdl-36326109

RESUMEN

Trace acetone determination in breath can be regarded as a noninvasive method for diagnosis of diabetes. Here, a paper-based CL gas sensor combined with UiO-66 as the preconcentrator was established for sensitive detection of trace acetone in exhaled breath. UiO-66 with excellent adsorption performance and unique water stability was used for the adsorption and enrichment of acetone gas under high humidity conditions in exhaled breath. As acetone can remarkably increase the chemiluminescence (CL) of the 2,4-dinitrophenylhydrazine (DNPH)-potassium permanganate (KMnO4) system, a sensitive CL device based on a paper substrate for trace acetone detection was established and the detection limit was 0.03 ppm. The fabricated method was used to assess the content of trace acetone in exhaled breath with satisfactory recoveries of 90-110%. It is expected to realize the noninvasive determination of acetone for diabetic patients in exhaled breath.


Asunto(s)
Diabetes Mellitus , Estructuras Metalorgánicas , Humanos , Acetona/química , Pruebas Respiratorias/métodos , Luminiscencia , Diabetes Mellitus/diagnóstico
15.
Small ; 18(42): e2203715, 2022 10.
Artículo en Inglés | MEDLINE | ID: mdl-36058648

RESUMEN

Limited by the insufficient active sites and the interference from breath humidity, designing reliable gas sensing materials with high activity and moisture resistance remains a challenge to analyze human exhaled breath for the translational application of medical diagnostics. Herein, the dual sensing and cooperative diagnosis is achieved by utilizing metal-organic frameworks (MOFs) and its derivative. The Fe-MIL-101-NH2 serves as the quartz crystal microbalance humidity sensing layer, which exhibits high selectivity and rapid response time (16 s/15 s) to water vapor. Then, the Co2+ and Ni2+ cations are further co-doped into Fe-MIL-101-NH2 host to obtain the derived Co/Ni/Fe trimetallic  oxides (CoNiFe-MOS-n). The chemiresistive CoNiFe-MOS-n sensor displays the high sensitivity (560) and good selectivity to acetone, together with a lower original resistance compared with Fe2 O3 and NiFe2 O4 . Moreover, as a proof-of-concept application, synergistic integration of Fe-MIL-101-NH2 and derived CoNiFe-MOS-n is carried out. The Fe-MIL-101-NH2 is applied as moisture sorbent materials, which realize a sensitivity compensation of CoNiFe-MOS-n sensors for the detection of acetone (biomarker gas of diabetes). The findings provide an insight for effective utilization of MOFs and the derived materials to achieve a trace gas detection in exhaled breath analysis.


Asunto(s)
Estructuras Metalorgánicas , Materiales Inteligentes , Humanos , Estructuras Metalorgánicas/química , Óxidos , Acetona/química , Vapor , Cationes , Biomarcadores
16.
J Am Soc Mass Spectrom ; 33(10): 1982-1989, 2022 Oct 05.
Artículo en Inglés | MEDLINE | ID: mdl-36126229

RESUMEN

The Paternò-Büchi (PB) reaction is a cycloaddition reaction between a carbon-carbon double bond (C═C) and a photochemically excited carbonyl-containing compound. The constrained ring formed between the C═C bond and the PB reagent is more susceptible to fragmentation by collision-induced dissociation, which facilitates identification of the C═C position within the fatty acyl tails of lipids. Although the original PB reaction using acetone had a low yield of derivatized lipids and therefore a low yield of diagnostic ions, a new generation of PB reagents based on halogenated acetophenones has improved the reaction yield substantially. In this study, we investigated the use of halogenated PB reagents and ion mobility to improve the identification of PB-derivatized lipids by shifting them out of the densely populated lipid region of ion mobility-mass spectrometry (IM-MS) space. Several halogenated PB reagents containing fluorine, chlorine and bromine were investigated for their ability to decrease the collision cross-section (CCS) values of derivatized lipids and yield sufficient intensity for both the derivatized lipid and its diagnostic ions. We found that 4'-chloro-2',6'-difluoroacetophenone (CDFAP) displayed the best performance, with an average decrease in CCS of 4.4% and yield of derivatized lipids and diagnostic ions comparable to the trifluorinated acetophenone reagent proposed by the Xia group. The unique isotope pattern resulting from the chlorine substituent aided in identification of the derivatized lipids and their diagnostic ions, as well. We further demonstrate that derivatization with CDFAP preserves the separation of lipids classes in IM-MS space.


Asunto(s)
Acetona , Bromo , Acetona/química , Acetofenonas , Carbono/química , Cloro , Flúor , Indicadores y Reactivos , Iones , Isótopos , Lípidos/química
17.
Anal Chem ; 94(38): 13117-13125, 2022 09 27.
Artículo en Inglés | MEDLINE | ID: mdl-36121000

RESUMEN

The evaluation of double bond positions in fatty acyl chains has always been of great concern given their significance in the chemical and biochemical role of lipids. Despite being the foremost technique for lipidomics, it is difficult in practice to obtain identification beyond the fatty acyl level by the sole high-resolution mass spectrometry. Paternò-Büchi reactions of fatty acids (FAs) with ketones have been successfully proposed for pinpointing double bonds in FAs in combination with the collision-induced fragmentation technique. In the present paper, an aza-Paternò-Büchi (aPB) reaction of lipids with 6-azauracil (6-AU) was proposed for the first time for the determination of carbon-carbon double bonds in fatty acyl chains using higher collisional dissociation in the negative ion mode. The method was optimized using free FA and phospholipid analytical standards and compared to the standard Paternò-Büchi reaction with acetone. The introduction of the 6-AU moiety allowed enhancing the ionization efficiency of the FA precursor and diagnostic product ions, thanks to the presence of ionizable sites on the derivatizing agent. Moreover, the aPB derivatization allowed the obtention of deprotonated ions of phosphatidylcholines, thanks to an intramolecular methyl transfer from the phosphocholine polar heads during ionization. The workflow was finally applied for pinpointing carbon-carbon double bonds in 77 polar lipids from an yeast (Saccharomyces cerevisiae) extract.


Asunto(s)
Acetona , Carbono , Acetona/química , Carbono/química , Ácidos Grasos , Iones , Fosfatidilcolinas , Fosfolípidos/química , Fosforilcolina , Extractos Vegetales
18.
Phys Chem Chem Phys ; 24(34): 20491-20505, 2022 Aug 31.
Artículo en Inglés | MEDLINE | ID: mdl-35993356

RESUMEN

The detection of volatile organic compounds by gas sensors is of great interest for environmental quality monitoring and the early-stage and noninvasive diagnosis of diseases. Experiments found hexane, toluene, aniline, butanone, acetone, and propanol gases in the exhaled breath of patients suffering from COVID-19, lung cancer, and diabetes. However, no studies are available to systematically elucidate the selectivity of these gases on nanosheets of zinc oxide for chemiresistive and direct thermoelectric gas sensors. Therefore, this work performed the elucidation by studying the electronic, electrical, and thermal properties of the bilayered ZnO nanosheets with polar (0001) and non-polar (112̄0) surfaces under the adsorption of the gases. The interaction between the gases and the nanosheets belongs to two groups: electrostatic attraction and charge exchange. The second one occurs due to the peak resonance of the same type of orbitals between the substrates and the gases along the surface normal and the first one for the other cases. The characteristics of the Seebeck coefficient exhibited distinct selectivity of butanone and acetone.


Asunto(s)
COVID-19 , Compuestos Orgánicos Volátiles , Óxido de Zinc , Acetona/química , Butanonas , Gases , Humanos , Óxido de Zinc/química
19.
Environ Sci Pollut Res Int ; 29(53): 80646-80656, 2022 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-35723824

RESUMEN

The hierarchical porous composites (Beta/Dt) were prepared by secondary growth method using natural diatomite and beta zeolite. Moreover, XRD, SEM, and BET characterize the composite's composition, surface structure, and pore structure. The adsorbability of Beta/Dt was evaluated by adsorption of three common volatile organic compounds (VOCs) of the printing industry: acetone, ethyl acetate, and toluene. The results show that under the optimum preparation condition, the adsorption capacities of the three VOCs on Beta/Dt were about 3.5 times those of pure beta zeolite and 4.7-35.3 times those of diatomite, respectively. It indicates the synergistic adsorption effect between beta zeolite and diatomite. The superior adsorption capacity of Beta/Dt can be attributed to the suitable micropore size, the increase of the diffusion channels, and the chemical adsorption on modification diatomite. The adsorption of acetone, ethyl acetate, and toluene on Beta/Dt conformed to the pseudo-second-order kinetic model. In contrast, adsorption isotherms conformed to the Langmuir model, meaning that both physical and chemical adsorption occurred simultaneously during the adsorption process, and the adsorption belonged to the monolayer adsorption. The chemical adsorption mechanism can be ascribed to the nucleophilic reaction between the three VOCs (acetone, ethyl acetate, and toluene) and Beta/Dt with positive charges resulting from the modification diatomite. Furthermore, the composite could still keep more than 90% of the adsorption capacity of the original adsorbent after five regeneration cycles.


Asunto(s)
Compuestos Orgánicos Volátiles , Zeolitas , Tolueno/química , Adsorción , Zeolitas/química , Acetona/química , Compuestos Orgánicos Volátiles/química , Cinética
20.
J Colloid Interface Sci ; 621: 119-130, 2022 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-35452926

RESUMEN

To improve gas sensing performance of SnO2 sensor, a heterostructure constructed by SnO2 and SnSe2 is designed and synthesized via hydrothermal method and post thermal oxidation treatment. The obtained SnSe2/SnO2 composite nanoparticles demonstrate a special core-shell structure with SnO2 nanograins distributed in the shell and mixed SnSe2 and SnO2 nanograins in the core. Owning to the promoted charge transfer effect invited by SnSe2, the sensor based on SnSe2/SnO2 composite nanoparticles exhibit expressively enhanced acetone sensing performance compared to the pristine SnO2 sensor. At the working temperature of 300 °C, the SnSe2/SnO2 composite sensor with optimized composition exhibits superior sensing property towards acetone, including high response (10.77-100 ppm), low theoretical limit of detection (0.354 ppm), high selectivity and good reproducibility. Moreover, the sensor shows a satisfactory sensing performance in trace acetone gas detection under high humidity condition (relative humidity: 70-90%), making it a promising candidate to constructing exhaled breath sensors for acetone detection.


Asunto(s)
Diabetes Mellitus , Nanopartículas , Acetona/química , Humanos , Reproducibilidad de los Resultados , Compuestos de Estaño/química
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