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1.
Analyst ; 149(5): 1518-1526, 2024 Feb 26.
Artículo en Inglés | MEDLINE | ID: mdl-38265063

RESUMEN

Sodium nitrite is a commonly used preservative and color protectant in the food industry. Conventional analytical methods are highly susceptible to food matrix interference, time-consuming and costly. In this study, the ion cross-linking method was employed to prepare alginate hydrogel substrates, and phenosafranin was chosen as a single-molecule probe to analyze sodium nitrite. Our investigation centered on elucidating the effects of alginate and cross-linking ion concentrations on Raman signal characteristics. The optimal Raman response was observed in the precursor solution with 1% sodium alginate and 0.1 mol L-1 cross-linking ions. The relative standard deviations (RSDs) of the feature peaks from the three substrate batches ranged from 1.22% to 16.30%, attesting the robustness and consistency of the substrates. The signal reduction of the substrates after a four-week storage period remained below 10%, indicating that the substrates had good reproducibility and stability. The limits of detection (LODs) for sodium nitrite in extracts from cured meat, luncheon meat, and sliced ham were determined to range from 3.75 mg kg-1 to 8.11 mg kg-1, with low interference from the food matrix. The support vector machine algorithm was utilized to train and predict the data, which proved to be more accurate (98.6%-99.8% recovery) than the traditional linear regression model (81.9%-112.7% recovery) in predicting the spiked samples. The application of hydrogel-based surface-enhanced Raman spectroscopy (SERS) substrates for nitrite detection in food, combined with machine learning for regression prediction in data processing, collectively augmented the potential of SERS technology in the field of food analysis.


Asunto(s)
Productos de la Carne , Nitrito de Sodio , Nitrito de Sodio/farmacología , Espectrometría Raman/métodos , Hidrogeles , Reproducibilidad de los Resultados
2.
Int J Mol Sci ; 24(19)2023 Sep 28.
Artículo en Inglés | MEDLINE | ID: mdl-37834156

RESUMEN

The interaction mechanism of hemoglobin (Hb) with bisphenol A (BPA) in diabetic patients and the difference with healthy people have been studied using spectroscopic and molecular docking techniques at several glucose (Glc) concentration, with bovine hemoglobin (BHb) instead of Hb. It is found that Glc can interact with BHb-BPA and affect its molecular structure, resulting in an altered microenvironment for tyrosine (Tyr) and tryptophan (Trp) in BHb-BPA. It is also found that Glc can bind to BHb alone, and its effect on the molecular structure of BHb is weaker than that on the structure of BHb in BHb-BPA complex. The results of circular dichroism (CD) and Fourier transform infrared spectroscopy (FTIR) indicate that Glc causes an increase in the content of the α-helix and a decrease in that of the ß-sheet of BHb-BPA by 1.5-1.9% and 3.1%, respectively. The results of molecular docking show that Glc binds to BHb-BPA through hydrogen and hydrophobic bonds, and the position of binding differs from that of Glc binding to BHb alone, which may be attributed to the fact that BPA affects the protein molecular structure of BHb and has an effect on the binding of BHb to Glc. This study provides some theoretical basis for the mechanism of BPA toxicity in vivo for people with different blood glucose levels.


Asunto(s)
Glucosa , Hemoglobinas , Humanos , Simulación del Acoplamiento Molecular , Unión Proteica , Dicroismo Circular , Hemoglobinas/metabolismo , Espectrometría de Fluorescencia , Sitios de Unión , Termodinámica
3.
Food Chem ; 426: 136616, 2023 Nov 15.
Artículo en Inglés | MEDLINE | ID: mdl-37354580

RESUMEN

The influences of frozen-then-chilled storage of minced pork on the formation of advanced glycation end-products (AGEs) including Nε-carboxymethyllysine and Nε-carboxyethyllysine, and their corresponding α-dicarbonyl precursors (α-DPs; glyoxal and methylglyoxal) during storage and subsequent heating were investigated in comparison with chilled storage. During cold storage, the levels of AGEs, trichloroacetic acid-soluble peptides, and Schiff bases in minced pork continuously increased while α-DPs decreased. The 30 min heating (100 °C) resulted in 64-560% increase of AGEs in pork, corresponding with an increase of Schiff bases and decreases of α-DPs. Compared to the chilled storage, the frozen-then-chilled storage led to no significant difference (P > 0.05) on the levels of AGEs and α-DPs in raw or heat-treated pork, implying that the formation and thawing of ice crystals in pork during the frozen-then-chilled storage had minor to no effects on the formation of AGEs and their α-DPs.


Asunto(s)
Carne de Cerdo , Carne Roja , Animales , Porcinos , Carne Roja/análisis , Reacción de Maillard , Bases de Schiff , Calefacción , Productos Finales de Glicación Avanzada/química
4.
J Sci Food Agric ; 103(14): 7218-7226, 2023 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-37347840

RESUMEN

BACKGROUND: Flexible surface-enhanced Raman spectroscopy (SERS) substrates such as paper-based substrates show great potential for rapid detection of residual chemicals on food surfaces. However, controlling the density and distribution of metallic nanoparticles adsorbed on the paper is still challenging. RESULTS: The amount of gold (Au) nanospheres (51 ± 4 nm) attached on the filter paper modified with 3-aminopropyltriethoxysilane (APTES) was tunable, increasing as the level of APTES (2.5-15.0 g kg-1 ) applied for paper modification increased. Moreover, the Au nanospheres were relative evenly distributed on the filter paper modified with 2.5-10.0 g kg-1 of APTES, which resulted in excellent intra- and inter-reproducibility of SERS signals for pesticides including thiram, diquat dibromide, and paraquat dichloride (relative standard deviation = 2.2-10.1%). The modified paper-based substrate could be used to detect as low as 0.05-0.2 mg L-1 of pesticides in standard solutions, and as low as 5-20 ng cm-2 of residual pesticides on apple skins with minimum sample pretreatment. CONCLUSION: This paper-based substrate with tunable feature for the density and distribution of nanoparticles is applicable for rapid SERS detection of residual pesticides in fruits and vegetables. © 2023 Society of Chemical Industry.


Asunto(s)
Nanopartículas del Metal , Nanosferas , Plaguicidas , Plaguicidas/análisis , Espectrometría Raman/métodos , Oro/química , Reproducibilidad de los Resultados , Electricidad Estática , Nanopartículas del Metal/química
5.
Food Chem ; 419: 135962, 2023 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-37004364

RESUMEN

This study was to screen and quantify characteristic volatiles tied to the quality deterioration of reheated pork via simultaneously reheating (75 °C, 30 min) and collecting headspace volatiles of precooked pork (100 °C, 10 min; stored: 0 °C, 0-14 d) for GC-MS analysis. The concentrations of hexanal (6.05 ± 0.86-12.05 ± 0.44 mg/kg), (E)-2-octenal (1.54 ± 0.16-3.07 ± 0.08 mg/kg), (E,E)-2,4-heptadienal (1.52 ± 0.44-2.58 ± 0.31 mg/kg) and 8 other selected volatiles in reheated pork increased as the storage time of the precooked counterparts increased. The increase rate of hexanal was 2.9-199 times faster than that of other volatiles based on zero-order reaction fitting (R2 = 0.876-0.997). Results from clustering analysis of these volatiles were consistent with their formation pathways tied to lipid autooxidation. This simple approach, reheating and collecting volatiles of precooked meat concurrently, introduces a new possibility for standardizing volatile analysis of precooked meats required being reheated before consumption.


Asunto(s)
Carne de Cerdo , Carne Roja , Animales , Porcinos , Carne de Cerdo/análisis , Carne Roja/análisis , Aldehídos/análisis , Carne/análisis
6.
Foods ; 12(8)2023 Apr 19.
Artículo en Inglés | MEDLINE | ID: mdl-37107488

RESUMEN

Efficient methods for monitoring sulfonamides (SAs) in water and animal-source foods are of great importance to achieve environmental safety and protect human health. Here, we demonstrate a reusable and label-free electrochemical sensor for the rapid and sensitive detection of sulfamethizole based on an electropolymerized molecularly imprinted polymer (MIP) film as the recognition layer. To achieve effective recognition, monomer screening among four kinds of 3-substituted thiophenes was performed by computational simulation and subsequent experimental evaluation, and 3-thiopheneethanol was finally selected. MIP synthesis is very fast and green, and can be in situ fabricated on the transducer surface within 30 min in an aqueous solution. The preparation process of the MIP was characterized by electrochemical techniques. Various parameters affecting MIP fabrication and its recognition response were investigated in detail. Under optimized experimental conditions, good linearity in the range of 0.001-10 µM and a low determination limit of 0.18 nM were achieved for sulfamethizole. The sensor showed excellent selectivity, which can distinguish between structurally similar SAs. In addition, the sensor displayed good reusability and stability. Even after 7 days of storage, or being reused 7 times, higher than 90% of the initial determination signals were retained. The practical applicability of the sensor was also demonstrated in spiked water and milk samples at the nM determination level with satisfactory recoveries. Compared to relevant methods for SAs, this sensor is more convenient, rapid, economical, and eco-friendly, and had comparable or even higher sensitivity, which offered a simple and efficient method for SA detection.

7.
J Mol Model ; 29(3): 81, 2023 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-36856830

RESUMEN

CONTEXT: The Maillard reaction is a high-temperature reaction of amino acids and carbohydrates to produce macromolecular substances such as melanoidins and intermediate reducing ketones, aldehydes, and volatile compounds. At present, only very limited researches involved the reaction mechanisms of Maillard reaction, which causes a lot of confusion in understanding numerous food processes. The detailed calculations of Maillard reaction are urgently needed. METHODS: The density functional theory (DFT) method (M06-2X/6-311G*) was used to deeply explore the specific mechanism of the primary and intermediate stages of Maillard reaction for a selected model system. RESULTS: The results show that the basic reaction processes in primary stage are the formation of Schiff-base by the condensation of amino and carbonyl groups, and then, Schiff-base tautomerization twice through proton transfer to generate Amadori rearrangement products. In the intermediate stage, two main reaction paths, 1-2 and 2-3 enolization, were comprehensively investigated. The first route finally generates 5-hydroxymethylfurfural through isomerization, dehydration, hydrolysis, elimination, and condensation, and the second route products dicarbonyl compounds through isomerization and elimination and then Strecker degradation forms aldehydes through condensation, decarboxylation, hydrolysis, and elimination. The results show that both paths are involved in complex reactions, some are lower barrier reactions, and some higher barrier reactions. An important aspect is that water catalysis is critical in all of these reactions; it is present in most processes. Our study deepens the understanding of the Maillard reaction from molecular level and facilitate the regulation of some harmful products.

8.
Spectrochim Acta A Mol Biomol Spectrosc ; 292: 122432, 2023 May 05.
Artículo en Inglés | MEDLINE | ID: mdl-36753866

RESUMEN

Concerns about food safety have been arisen due to the improper use of chemicals in aquaculture. Malachite green (MG) has attracted attention because of its illegal usage and its potential negative impacts on the environment and public health. Surface-enhanced Raman scattering (SERS) platforms coupled with different SERS substrates have been employed for rapid analysis of MG residues in food. However, the most commonly used SERS substrates were non-reusable and showed limited detection sensitivity. In this study, a novel SERS substrate with a good recyclability and a high sensitivity was prepared by electrostatically assembling together a metal-organic framework material called materials of institute lavoisie-100(Fe) (MIL-100(Fe)) and Au NPs. The lowest detectable concentration of MG was 10-13 M based on the optimal substrate. The SERS sensor was applied for the detection of the trace MG in fish pond water, which was accomplished with the correlation coefficients R2 = 0.991-0.996 in a concentration range of 10-6-10-13 M. Moreover, MIL-100(Fe)/Au was recycled at least five times, realizing a "detection to degradation", showing great potential for food contamination monitoring due to its distinguished performance.


Asunto(s)
Nanopartículas del Metal , Espectrometría Raman , Animales , Estanques/análisis , Colorantes de Rosanilina/análisis , Peces , Agua/análisis , Oro/química , Nanopartículas del Metal/química
9.
Foods ; 11(18)2022 Sep 12.
Artículo en Inglés | MEDLINE | ID: mdl-36140939

RESUMEN

This study aimed to evaluate the effects of lactic acid (LA), citric acid (CA), and malic acid (MA) varying in concentration (0.5−2.0% w/w) on the rheological properties of fish gelatin (1.5−6.67% w/w) obtained from the skin of tilapia (Oreochromis mossambicus). The addition of LA, CA, or MA in gelatin dispersions significantly (p < 0.05) weakened their gel strengths, leading to a 14.3−62.2 reduction in gel strength. The gel strength, elastic (G'), and viscous (G″) moduli, as well as the gelling (TG) and melting (TM) temperatures of gelatin dispersions decreased with an increased level of acid added, implying the weakening effects of these acids on junction zones of the gelatin network in aqueous media. The addition of LA had less effect on these rheological properties of gelatin dispersions as compared to that of MA and CA, which were consistent with their effects on the pH of gelatin dispersions. Moreover, the reductions of TG and TM for gelatin dispersions with a higher gelatin concentration (e.g., 6.67% gelatin with 0.5% LA, TG dropped 0.4 °C) due to the addition of LA, CA, or MA were less pronounced compared to those with a lower gelatin content (e.g., 2% gelatin with 0.5% LA, TG dropped 7.1 °C), likely attributing to the stronger buffering effect of the high gelatin dispersion and less percentage reduction in the junction zones in the dispersion due to the addition of an acid. Incorporation of the effects of acids on the linear relationships (R2 = 0.9959−0.9999) between the square of gelatin concentrations and G' or G″ could make it possible to develop a model to predict G', G″, phase transition temperatures of gelatin dispersions containing different amounts of gelatin and acid (within the tested range) in the future.

10.
J Sci Food Agric ; 102(14): 6211-6219, 2022 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-35478166

RESUMEN

BACKGROUND: Surface-enhanced Raman scattering (SERS) substrates based on metallic nanoparticles locked in some flexible materials have great potential for rapid detection of pesticide residues in foods, but these substrates are generally not reusable. RESULTS: A bendable and reusable sponge based on polydimethylsiloxane (PDMS) and Au nanospheres was synthesized and employed as SERS substrate to analyze thiram on the surfaces of apples and grapes (20-1000 ng cm-2 ) and in their juices (0.5-5.0 mg L-1 ) with minimum sample pretreatments. The lowest detectible concentrations for thiram in fruit juices and on fruit skins were 0.5 mg L-1 and 20 ng cm-2 , respectively. The Au-PDMS substrate had acceptable intra-reproducibility for SERS analysis of thiram in fruit juices and on fruit skins, resulting in 3.6-16.9% relative standard deviation (RSD) for the SERS signal of the primary peak of thiram. Moreover, the Au-PDMS substrate exhibited distinguished reusability and stability, which could provide a reproducible SERS signal of thiram in apple juice even after the substrate being reused ten times (RSDs for the three major characteristic peaks of thiram were 2.7-10.5% during the ten reused cycles). CONCLUSION: This flexible and reusable Au-PDMS SERS substrate for thiram detection could be readily extended to the analysis of other trace chemicals in a broad range of foods, providing a new possibility for SERS application. © 2022 Society of Chemical Industry.


Asunto(s)
Malus , Nanopartículas del Metal , Residuos de Plaguicidas , Dimetilpolisiloxanos , Frutas/química , Oro/química , Malus/química , Nanopartículas del Metal/química , Residuos de Plaguicidas/análisis , Reproducibilidad de los Resultados , Espectrometría Raman/métodos , Tiram
11.
Chemphyschem ; 23(9): e202200001, 2022 05 04.
Artículo en Inglés | MEDLINE | ID: mdl-35266268

RESUMEN

The spontaneous interconversion between covalent forces and noncovalent counterparts remains an unexplained mystery to date. Here we have discovered a marvelous transformation between them through halogen bonding using NI3 as a prototype. Our results show that the interaction strength of the NI3 dimer is 7.01 kcal mol-1 , demonstrating that it is a quite strong halogen bond. Molecular orbital analyses indicate that the frontier molecular orbitals result from strong mixing of the fragment orbitals, which may be the electronic structure basis for interconversion. Further studies on a series of NI3 oligomers (5-, 10-, 15-, 20-, 26-, 30-mer) show that the interconversion occurs approximately at 26-mer on the basis on bond distance, ELF, etc.; the interconversion is a gradual transformation and not a sudden one. This study provides more insights into the halogen bonding and the high explosivity of NI3 containing species.


Asunto(s)
Halógenos , Halógenos/química , Enlace de Hidrógeno
12.
J Food Biochem ; 45(9): e13872, 2021 09.
Artículo en Inglés | MEDLINE | ID: mdl-34296449

RESUMEN

Dipeptidyl peptidase-IV (DPP-IV) inhibitors can reduce the blood sugar levels of diabetic patients by preventing the rapid decomposition of incretin hormone and prolonging its physiological effects. In this study, DPP-IV inhibitory peptides FAGDDAPR and LAPPRGSL were isolated from defatted Antarctic krill powder (DAKP) protein by the sequential purification of ultrafiltration, gel filtration chromatography, and RP-HPLC, and IC50 values of the two peptides were 349.70 ± 3.66 µM and 461.14 ± 0.87 µM, respectively. The FAGDDAPR and LAPPRGSL were identified by LC-MS/MS method, and the molecular models of DPP-IV and the two peptides were further constructed by AutoDock Vina software, the results revealed that the inhibition activity of FAGDDAPR and LAPPRGSL was mainly attributed to the formation of strong hydrophobic interactions and hydrogen bonds with amino acids of DPP-IV. PRACTICAL APPLICATIONS: DAKP is an economical by-product produced in the production of krill oil and contains high-quality protein, but these products were mainly used as fish feed and had low utility value in the past. DPP-IV inhibitors are an efficacious drug employed in the treatment of hyperglycemia processes. However, these drugs can cause undesirable side effects. Thus, the development of new natural hypoglycemic drugs with low side effects is a valuable strategy to be applied in therapeutic interventions.


Asunto(s)
Euphausiacea , Animales , Cromatografía Liquida , Humanos , Péptidos , Polvos , Espectrometría de Masas en Tándem
13.
J Food Prot ; 83(11): 1871-1876, 2020 Nov 01.
Artículo en Inglés | MEDLINE | ID: mdl-32559280

RESUMEN

ABSTRACT: The effects of salt treatment (2% [w/w] low salt and 6% [w/w] high salt) and storage time (0 to 12 days) on two biogenic amines (histamine and tyramine), total volatile base nitrogen (TVB-N), pH, and volatile compounds of the North Pacific squid during storage at 4°C were evaluated. The freshness of squid muscle was evaluated by monitoring the changes in these indicators during storage. Results showed that histamine and tyramine contents increased with storage time (4.29 to 22.47 mg/kg for histamine and 28.10 to 135.78 mg/kg for tyramine) and that, in samples treated with salt, formation of these amines can be effectively inhibited (P < 0.05) compared with untreated samples. The overall pH level initially decreased and then increased during storage (ranging from 6.49 to 7.13), and the pH level of the two salt treatment groups was a little lower than that of the control group. The TVB-N value increased with time and was effectively inhibited by salt (P < 0.05). The number and content of the volatile components in squid varied during the entire storage time. The main volatile components detected in North Pacific squid were aliphatic hydrocarbons, alcohols, aldehydes, ketones, acids, esters, aromatic hydrocarbons, phenols, nitrogenous compounds, sulfo compounds, and esters. Several compounds, such as trimethylamine, butyric acid, and sulfureted hydrogen, can be used to determine the quality of aquatic products, and salt treatment can inhibit their formation. The TVB-N value was significantly correlated with pH level and with the concentrations of histamine, tyramine, and several volatile compounds in all samples (P < 0.05). In summary, salt concentration had a positive effect on extending the shelf life of North Pacific squid, and multiple indicators should be used to determine the quality of squid.


Asunto(s)
Decapodiformes , Conservación de Alimentos , Animales , Aminas Biogénicas/análisis , Alimentos Marinos/análisis , Cloruro de Sodio
14.
J Food Sci ; 85(7): 2090-2097, 2020 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-32579728

RESUMEN

The inhibitory effects of vitamins (nicotinic acid, pyridoxamine [PM], and l-ascorbic acid) and phenolic acids (ferulic acid and p-coumaric acid) on the formation of 2-amino-3,8-dimethylimidazo [4,5-f] quinoxaline (MeIQx) were studied in a glycine/glucose/creatinine model system and fried tilapia cakes. The results showed that PM was the most potential inhibitor and the inhibition rates reached 82.72% and 78.54% in model system and fried tilapia cakes, respectively. Detailed formation mechanism of MeIQx was put forward to find the inevitable species in the non-free radical formation mechanism of MeIQx. Dose-dependent analysis of PM on methylglyoxal (MGO ) and MeIQx formation were studied by using model systems and the results showed that MGO and MeIQx were both reduced about 60% in reaction mixtures when the molar ratio of PM to glycine was 1:16, which indicated that MGO is a key intermediate on the pathway of MeIQx formation. Quantum chemistry calculations showed that PM can act as a useful inhibitor to inhibit the formation of MeIQx and react with MGO to form new compounds. A pathway for the inhibitory activity of PM against MeIQx formation was proposed. PRACTICAL APPLICATION: Pyridoxamine was the most effective inhibitor against heterocyclic aromatic amines (HAAs) and could be applied to a variety of food systems. While the inhibitory mechanism is still unclear. Detailed formation mechanism of MeIQx was put forward first and suggested methylglyoxal as an inevitable species in the non-free radical formation mechanism of MeIQx in this study. Pyridoxamine trapping methylglyoxal is likely a key mechanism against the generation of MeIQx was demonstrated by quantum chemistry calculation and experimental demonstration. These findings may provide effective suggestions for reducing HAAs and similar toxicants in daily cuisine.


Asunto(s)
Piruvaldehído/química , Quinoxalinas/química , Vitaminas/química , Aminas/química , Animales , Culinaria , Productos Pesqueros/análisis , Calor , Hidroxibenzoatos/química , Mutágenos/metabolismo , Piridoxamina/química , Tilapia
15.
Nano Lett ; 20(4): 2507-2513, 2020 04 08.
Artículo en Inglés | MEDLINE | ID: mdl-32182075

RESUMEN

Plasmon-mediated photocatalysis provides a novel strategy for harvesting solar energy. Identification of the rate-determining step and its activation energy in plasmon-mediated photocatalysis plays critical roles for understanding the contribution of hot carriers, which facilitates rational designation of catalysts with integrated high photochemical conversion efficiency and catalytic performance. However, it remains a challenge due to a lack of research tools with spatiotemporal resolution that are capable of capturing intermediates. In this work, we used a single-molecule fluorescence approach to investigate a localized surface plasmon resonance (LSPR)-enhanced photocatalytic reaction with subturnover resolution. By introducing variable temperature as an independent parameter in plasmonic photocatalysis, the activation energies of tandem reaction steps, including intermediate generation, product generation, and product desorption, were clearly differentiated, and intermediate generation was found to be the rate-limiting step. Remarkably, the cause of the plasmon-enhanced catalysis performance was found to be its ability of lowering the activation energy of intermediate generation. This study gives new insight into the photochemical energy conversion pathways in plasmon-enhanced photocatalysis and sheds light on designing high-performance plasmonic catalysts.


Asunto(s)
Energía Solar , Resonancia por Plasmón de Superficie , Termodinámica , Catálisis , Fluorescencia , Procesos Fotoquímicos , Luz Solar , Temperatura
16.
Phys Chem Chem Phys ; 21(47): 26232-26236, 2019 Dec 21.
Artículo en Inglés | MEDLINE | ID: mdl-31764929

RESUMEN

A unique noncovalent interaction between XeO3 and 18-crown-6 has been studied by density functional theory. The calculated results show that there exists an extremely strong binding force between both species, reaching 36.44 kcal mol-1, which is comparable to the strong cation-π interaction. Detailed analyses on relaxed force constants, electrostatic potentials and the independent gradient model, etc. suggest that both quite strong aerogen bondings (XeO) and relatively weak unconventional H-bondings (C-HO) coexist, and the complex is a typical heterodimer with multiple binding sites. Further studies found that XeO3 takes a quick rotary motion relative to 18-crown-6 in the complex due to low rotary barrier. Another two guest molecules, KrO3 and ArO3, are also discussed.

17.
Nano Lett ; 19(6): 4205-4210, 2019 06 12.
Artículo en Inglés | MEDLINE | ID: mdl-31145634

RESUMEN

Layer-by-layer growth played a critical role in the fine design of novel materials and devices. Although it has been widely studied during materials synthesis, the atomic mechanism of the growth remains unclear due to the lack of direct observation at the atomic scale. Here, we report a new mode in layer-by-layer growth via surface reconstruction on MoO2 (011) by environmental transmission electron microscopy and density functional theory calculations. Our in situ environmental transmission electron microscopy results demonstrate that the layer-by-layer growth of MoO2 experiences two steps that occur in an oscillatory manner: (1) the formation of an atomic ledge by transforming a section of the reconstructed layer to the intrinsic surface layer and then (2) the spontaneous reconstruction of the newly formed intrinsic surface section. Thus, the surface reconstruction can be considered as an intermediated phase during the layer-by-layer growth of MoO2. A similar phenomenon was also observed in the MoO2 dissolution procedure.

18.
J Phys Condens Matter ; 30(44): 444001, 2018 Nov 07.
Artículo en Inglés | MEDLINE | ID: mdl-30247144

RESUMEN

Aerogen bonding, as a specific noncovalent interaction, has attracted wide attention recently. A number of theoretical studies have proposed this effect based on the analysis of electronic structures of aerogen-containing systems though, the spectral characteristics have not been identified, which becomes the obstacle for the experimental confirmation of this interaction. In this paper, we employed the density functional theory to explore the energetic and geometric properties, infrared, Raman spectra of five small molecular clusters XeO3·H2O, XeO3·NH3, XeO3 dimer, XeO3 trimer, and XeO3·2H2O. Our results show the binding energies of the most favorable conformations for the dimers are larger than -10.00 kcal mol-1 and those for trimers are larger than -20.00 kcal mol-1, which indicates the strong aerogen bonding is favorable for the stabilities of these clusters. More importantly, some new IR and Raman vibrations at fingerprint region (<1000 cm-1) are identified, which corresponds to the formation of aerogen bonds. This study provides a viable way for the experimentalists to characterize the aerogen bonding in future.

19.
Small ; 14(12): e1703510, 2018 03.
Artículo en Inglés | MEDLINE | ID: mdl-29457350

RESUMEN

Surface plasmon resonance of coinage metal nanoparticles is extensively exploited to promote catalytic reactions via harvesting solar energy. Previous efforts on elucidating the mechanisms of enhanced catalysis are devoted to hot electron-induced photothermal conversion and direct charge transfer to the adsorbed reactants. However, little attention is paid to roles of hot holes that are generated concomitantly with hot electrons. In this work, 13 nm spherical Au nanoparticles with small absorption cross-section are employed to catalyze a well-studied glucose oxidation reaction. Density functional theory calculation and X-ray absorption spectrum analysis reveal that hot holes energetically favor transferring catalytic intermediates to product molecules and then desorbing from the surface of plasmonic catalysts, resulting in the recovery of their catalytic activities. The studies shed new light on the use of the synergy of hot holes and hot electrons for plasmon-promoted catalysis.

20.
Chemistry ; 22(8): 2586-9, 2016 Feb 18.
Artículo en Inglés | MEDLINE | ID: mdl-26699400

RESUMEN

The interaction between a noble gas atom and an aromatic π-electron system, which mainly originates from the London dispersion force, is very weak and has not attracted enough attention yet. Herein, we reported a type of notably enhanced aerogen-π interaction between cation-π systems and noble gas atoms. The binding strength of a divalent cation-π system with a xenon atom is comparable to a moderate hydrogen bond (up to ca. 7 kcal mol(-1)), whereas krypton and argon atoms produce slightly weaker interactions. Energy-decomposition analysis reveals that the induction interaction is responsible for the stabilization of divalent cation-π⋅Xe species besides the dispersion interaction. Our results might be helpful to increase the understanding of some unsolved mysteries of aerogens.

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