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1.
Sci Adv ; 10(12): eadl0849, 2024 Mar 22.
Artigo em Inglês | MEDLINE | ID: mdl-38517965

RESUMO

Icy moons like Enceladus, and perhaps Europa, emit material sourced from their subsurface oceans into space via plumes of ice grains and gas. Both moons are prime targets for astrobiology investigations. Cassini measurements revealed a large compositional diversity of emitted ice grains with only 1 to 4% of Enceladus's plume ice grains containing organic material in high concentrations. Here, we report experiments simulating mass spectra of ice grains containing one bacterial cell, or fractions thereof, as encountered by advanced instruments on board future space missions to Enceladus or Europa, such as the SUrface Dust Analyzer onboard NASA's upcoming Europa Clipper mission at flyby speeds of 4 to 6 kilometers per second. Mass spectral signals characteristic of the bacteria are shown to be clearly identifiable by future missions, even if an ice grain contains much less than one cell. Our results demonstrate the advantage of analyses of individual ice grains compared to a diluted bulk sample in a heterogeneous plume.


Assuntos
Meio Ambiente Extraterreno , Júpiter , Gelo , Exobiologia/métodos , Oceanos e Mares
2.
Angew Chem Int Ed Engl ; 63(4): e202314784, 2024 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-37917653

RESUMO

Despite being recognized primarily as an analytical technique, mass spectrometry also has a large potential as a synthetic tool, enabling access to advanced synthetic routes by reactions in charged microdroplets or ionic thin layers. Such reactions are special and proceed primarily at surfaces of droplets and thin layers. Partial solvation of the reactants is usually considered to play an important role for reducing the activation barrier, but many mechanistic details still need to be clarified. In our study, we showcase the synergy between two sequentially applied "preparative mass spectrometry" methods: initiating accelerated reactions within microdroplets during electrospray ionization to generate gaseous ionic intermediates in high abundance, which are subsequently mass-selected and soft-landed to react with a provided reagent on a substrate. This allows the generation of products at a nanomolar scale, amenable to further characterization. In this proof-of-concept study, the contrasting reaction pathways between intrinsically neutral and pre-charged reagents, respectively, both in microdroplets and in layers generated by ion soft-landing are investigated. This provides new insights into the role of partially solvated reagents at microdroplet surfaces for increased reaction rates. Additionally, further insights into reactions of ions of the same polarity under various conditions is obtained.

3.
RSC Adv ; 13(47): 32928-32938, 2023 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-38025853

RESUMO

The existence of endocrine disrupting chemicals (EDCs) in water and wastewater gives rise to significant environmental concerns. Conventional treatment approaches demonstrate limited capacity for EDC removal. Thus, incorporation of advanced separation procedures becomes essential to enhance the efficiency of EDC removal. In this work, adsorber composite microfiltration polyethersulfone membranes embedded with divinyl benzene polymer particles were created. These membranes were designed for effectively removing a variety of EDCs from water. The adsorber particles were synthesized using precipitation polymerization. Subsequently, they were integrated into the membrane scaffold through a phase inversion process. The technique of electron beam irradiation was applied for the covalent immobilization of particles within the membrane scaffold. Standard characterization procedures were carried out (i.e., water permeance, contact angle, X-ray photoelectron spectroscopy and scanning electron microscopy) to gain a deep understanding of the synthesized membrane properties. Dynamic adsorption experiments demonstrated the excellent capability of the synthesized composite membranes to effectively remove EDCs from water. Particularly, among the various target molecules examined, testosterone stands out with the most remarkable enhancement, presenting an adsorption loading of 220 mg m-2. This is an impressive 26-fold increase in the adsorption when compared to the performance of the pristine membrane. Similarly, androst-4-ene-3,17-dione exhibited an 18-fold improvement in adsorption capacity in comparison to the pristine membrane. The composite membranes also exhibited significant adsorption capacities for other key compounds, including 17ß-estradiol, equilin, and bisphenol-A. With the implementation of an effective regeneration procedure, the composite membranes were put to use for adsorption over three consecutive cycles without any decline in their adsorption capacity.

4.
ACS Nano ; 17(16): 15401-15410, 2023 Aug 22.
Artigo em Inglês | MEDLINE | ID: mdl-37440601

RESUMO

Today's huge amount of data generation and transfer induced an urgent requirement for long-term data storage. Here, we demonstrate and discuss a concept for long-term storage using NV centers inside nanodiamonds. The approach is based upon the radiation-induced generation of additional vacancies (so-called GR1 states), which quench the initial NV centers, resulting in a reduced overall fluorescence lifetime of the NV center. Using the tailored fluorescence lifetime of the NV center to code the information, we demonstrate a "beyond binary" data storage density per bit. We also demonstrate that this process is reversible by heating the sample or the spot of information. This proof of principle shows that our technique may be a promising alternative data storage technology, especially in terms of long-term storage, due to the high stability of the involved color centers. In addition to the proof-of-principle demonstration using macroscopic samples, we suggest and discuss the usage of focused electron beams to write information in nanodiamond materials, to read it out with focused low-intensity light, and to erase it on the macro-, micro-, or nanoscale.

5.
Photochem Photobiol Sci ; 22(9): 2143-2151, 2023 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-37277672

RESUMO

Water-insoluble organic UV filters like tris-biphenyl-triazine (TBPT) can be prepared as aqueous dispersions of nanoparticles. The particles consist of the respective UV absorber molecules and show strong UV absorbance. Since there is a certain solubility of such UV absorbers in organic solvents, it is possible to measure the absorbance spectrum also in solution, for instance in ethanol or dioxane. The UV spectrum of the aqueous dispersion shows a slight hypsochromic shift of the original band with an additional shoulder at longer wavelengths. For the understanding of the observed changes of UV-Vis spectra of this UV absorber, either dissolved in an organic solvent or dispersed as nanoparticles in water, DFT calculations were carried out with the respective monomer and aggregates of TBPT molecules in the different media. The calculated UV-Vis spectra of isolated, that means dissolved, TBPT molecules in ethanol and in dioxane agree well with experimentally observed ones. The observed changes in the shape of experimental UV-Vis spectra in aqueous dispersion cannot be explained with a solvent effect only. It was found that the studied molecules could form stable energetically favorable π-stacked aggregates, which show UV-Vis spectra in reasonable agreement with those experimentally observed in aqueous dispersion. Such aggregates of TBPT are most likely the reason for the observed additional shoulder in the UV/vis absorbance spectrum. In addition, the mechanism of the photochemical deactivation of excited TBPT molecules was studied in detail with TD DFT in dioxane and in water.

6.
Nature ; 618(7965): 489-493, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-37316718

RESUMO

Saturn's moon Enceladus harbours a global1 ice-covered water ocean2,3. The Cassini spacecraft investigated the composition of the ocean by analysis of material ejected into space by the moon's cryovolcanic plume4-9. The analysis of salt-rich ice grains by Cassini's Cosmic Dust Analyzer10 enabled inference of major solutes in the ocean water (Na+, K+, Cl-, HCO3-, CO32-) and its alkaline pH3,11. Phosphorus, the least abundant of the bio-essential elements12-14, has not yet been detected in an ocean beyond Earth. Earlier geochemical modelling studies suggest that phosphate might be scarce in the ocean of Enceladus and other icy ocean worlds15,16. However, more recent modelling of mineral solubilities in Enceladus's ocean indicates that phosphate could be relatively abundant17. Here we present Cassini's Cosmic Dust Analyzer mass spectra of ice grains emitted by Enceladus that show the presence of sodium phosphates. Our observational results, together with laboratory analogue experiments, suggest that phosphorus is readily available in Enceladus's ocean in the form of orthophosphates, with phosphorus concentrations at least 100-fold higher in the moon's plume-forming ocean waters than in Earth's oceans. Furthermore, geochemical experiments and modelling demonstrate that such high phosphate abundances could be achieved in Enceladus and possibly in other icy ocean worlds beyond the primordial CO2 snowline, either at the cold seafloor or in hydrothermal environments with moderate temperatures. In both cases the main driver is probably the higher solubility of calcium phosphate minerals compared with calcium carbonate in moderately alkaline solutions rich in carbonate or bicarbonate ions.

7.
Artigo em Inglês | MEDLINE | ID: mdl-37174267

RESUMO

In this study, a valuable adsorbent was functionalized using commercial ZnO and a mango seed extract (MS-Ext) as a green approach for synthesis. Fourier-transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, and energy-dispersive X-ray analysis spectraconfirmed the presence of bioactive phenolic compounds and Cu2+ ions on the surface of ZnO. Functionalized Cu-doped ZnO/MS-Ext exhibits high efficacy in acidic, neutral, and alkaline medium, as indicated by 98.3% and 93.7% removal of methylene blue (MB) and crystal violet (CV) dyes, respectively. Cu-doped ZnO/MS-Ext has a zeta potential significantly lower than pristine zinc oxide (p-ZnO), which results in enhanced adsorption of cationic MB and CV dyes. In binary systems, both MB and CV were significantly removed in acidic and alkaline media, with 92% and 87% being removed for CV in acidic and alkaline media, respectively. In contrast, the removal efficiency of methyl orange dye (MO) was 16.4%, 6.6% and 11.2% for p-ZnO, ZnO/Ext and Cu-doped ZnO/Ext, respectively. In general, the adsorption kinetics of MB on Cu-doped ZnO/MS-Ext follow this order: linear pseudo-second-order (PSO) > nonlinear pseudo-second-order (PSO) > nonlinear Elovich model > linear Elovich model. The Langmuir isotherm represents the adsorption process and indicates that MB, CV, and MO are chemisorbed onto the surface of the adsorbent at localized active centers of the MS-extract functional groups. In a binary system consisting of MB and CV, the maximum adsorption capacity (qm) was 72.49 mg/g and 46.61 mg/g, respectively. The adsorption mechanism is governed by electrostatic attraction and repulsion, coordination bonds, and π-π interactions between cationic and anionic dyes upon Cu-doped ZnO/Ext surfaces.


Assuntos
Poluentes Químicos da Água , Óxido de Zinco , Óxido de Zinco/química , Adsorção , Corantes/química , Violeta Genciana , Cátions/química , Poluentes Químicos da Água/análise , Cinética , Concentração de Íons de Hidrogênio
8.
Curr Opin Biotechnol ; 81: 102948, 2023 06.
Artigo em Inglês | MEDLINE | ID: mdl-37163825

RESUMO

Rapid prototyping of microfluidic chips is a key enabler for controlled biotechnology applications in microspaces, as it allows for the efficient design and production of microfluidic systems. With rapid prototyping, researchers and engineers can quickly create and test new microfluidic chip designs, which can then be optimized for specific applications in biotechnology. One of the key advantages of microfluidic chips for biotechnology is the ability to manipulate and control biological samples in a microspace, which enables precise and controlled experiments under well-defined conditions. This is particularly useful for applications such as cell culture, drug discovery, and diagnostic assays, where precise control over the biological environment is crucial for obtaining accurate results. Established methods, for example, soft lithography, 3D printing, injection molding, as well as other recently highlighted innovative approaches, will be compared and challenges as well as limitations will be discussed. It will be shown that rapid prototyping of microfluidic chips enables the use of advanced materials and technologies, such as smart materials and digital sensors, which can further enhance the capabilities of microfluidic systems for biotechnology applications. Overall, rapid prototyping of microfluidic chips is an important enabling technology for controlled biotechnology applications in microspaces, as well as for upscaling it into macroscopic bioreactors, and its continued development and improvement will play a critical role in advancing the field. The review will highlight recent trends in terms of materials and competing approaches and shed light on current challenges on the way toward integrated microtechnologies. Also, the possibility to easy and direct implementation of novel functions (membranes, functionalization of interfaces, etc.) is discussed.


Assuntos
Técnicas de Cultura de Células , Microfluídica , Microfluídica/métodos , Biotecnologia , Microtecnologia , Impressão Tridimensional
9.
J Am Soc Mass Spectrom ; 34(5): 878-892, 2023 May 03.
Artigo em Inglês | MEDLINE | ID: mdl-37018538

RESUMO

Small ice particles play an important role in atmospheric and extraterrestrial chemistry. Circumplanetary ice particles that are encountered by space probes at hypervelocities play a critical role in the determination of surface and subsurface properties of their source bodies. Here we present an apparatus for the generation of low-intensity beams of single mass-selected charged ice particles under vacuum. They are produced via electrospray ionization of water at atmospheric pressure and undergo evaporative cooling when transferred to vacuum through an atmospheric vacuum interface. m/z selection is achieved through two subsequent quadrupole mass filters operated in the variable-frequency mode within a range of m/z values between 8 × 104 and 3 × 107. Velocity and charge of the selected particles are measured using a nondestructive single-pass image charge detector. From the known electrostatic acceleration potentials and settings of the quadrupoles the particle masses could be obtained and be accurately controlled. It has been shown that the droplets are frozen within the transit time of the apparatus such that ice particles are present after the quadrupole stages and finally detected. The demonstrated correspondence between particle mass and specific quadrupole potentials in this device allows preparation of beams of single particles with a repetition rate between 0.1 and 1 Hz with various diameter distributions from 50 to 1000 nm at 30-250 eV of kinetic energy per charge. This corresponds to velocities and particle masses quickly available between 600 m/s (80 nm) and 50 m/s (900 nm) and particle charge numbers (positive) between 103 and 104[e], depending upon size.

10.
Chem Sci ; 14(14): 3730-3741, 2023 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-37035708

RESUMO

The self-assembly of peptides into supramolecular structures has been linked to neurodegenerative diseases but has also been observed in functional roles. Peptides are physiologically exposed to crowded environments of biomacromolecules, and particularly cellular membrane lipids. Previous research has shown that membranes can both accelerate and inhibit peptide self-assembly. Here, we studied the impact of membrane models that mimic cellular oxidative stress and compared this to mammalian and bacterial membranes. Using molecular dynamics simulations and experiments, we propose a model that explains how changes in peptide-membrane binding, electrostatics, and peptide secondary structure stabilization determine the nature of peptide self-assembly. We explored the influence of zwitterionic (POPC), anionic (POPG) and oxidized (PazePC) phospholipids, as well as cholesterol, and mixtures thereof, on the self-assembly kinetics of the amyloid ß (1-40) peptide (Aß40), linked to Alzheimer's disease, and the amyloid-forming antimicrobial peptide uperin 3.5 (U3.5). We show that the presence of an oxidized lipid had similar effects on peptide self-assembly as the bacterial mimetic membrane. While Aß40 fibril formation was accelerated, U3.5 aggregation was inhibited by the same lipids at the same peptide-to-lipid ratio. We attribute these findings and peptide-specific effects to differences in peptide-membrane adsorption with U3.5 being more strongly bound to the membrane surface and stabilized in an α-helical conformation compared to Aß40. Different peptide-to-lipid ratios resulted in different effects. We found that electrostatic interactions are a primary driving force for peptide-membrane interaction, enabling us to propose a model for predicting how cellular changes might impact peptide self-assembly in vivo.

11.
Phys Chem Chem Phys ; 25(16): 11732-11744, 2023 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-37066667

RESUMO

Precise, efficient, and effective control of chemical reaction conditions is a viable measure for the environment-conscious time and energy resource management in modern laboratories and in industry. Parameter changes such as surface enlargement, pH, local reactant accumulation by solvent evaporation and polarization effects, etc., have been shown to greatly affect the reaction rate of a chemical reaction. In electrospray (ES) ionization - a soft ionization method often used for mass spectrometry - all these parameters change constantly and with high dynamics during the nebulization process that generates droplets as the ultimate confined µ-reaction vessels. Therefore, high acceleration factors are reported in literature for a manifold of such µ-droplet reactions. Here, the tri-molecular Mannich reaction was identified as a suitable candidate for studying thermal, electronic, and fluidic manipulation of the ES process to achieve high conversion rates with short reaction times and compare them to the batch reaction. Some of these manipulations were conducted separately to better quantify their individual contributions. Here, the keto-enol-tautomerism of the used ß-diketones, the high proton concentrations, and the longer reaction times in the µ-droplets are presumed to have the greatest impact on these enhancement factors. Experiments were performed to find ES conditions with small initial droplets and long droplet flight times where the highest reaction conversion rates are obtained. A sharp increase in the product peak was found at large distances between the mass spectrometry (MS) inlet and ES source at high voltages. Moreover, different trends were found for the two ketones studied, acetylacetone (AcAc) and 1,3-cyclohexanedione (Cyclo), by changing the temperature of the heated ES source. Finally, high conversion rates were obtained for the combination of formaldehyde (Fal) and piperidine (Pip) with AcAc and Cyclo, respectively, with over 90%. With respect to the batch reaction, this is mainly due to an increase in reaction kinetics as well as a shift in thermodynamics for the µ-droplet reaction environment.

12.
Anal Chem ; 95(7): 3621-3628, 2023 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-36753610

RESUMO

The coupling of an Orbitrap-based mass analyzer to the laser-induced liquid beam ion desorption (LILBID) technique has been investigated, with the aim to reproduce the mass spectra recorded by Cassini's Cosmic Dust Analyzer (CDA) in the vicinity of Saturn's icy moon Enceladus. LILBID setups are usually coupled with time-of-flight (TOF) mass analyzers, with a limited mass resolution (∼800 m/Δm). Thanks to the Orbitrap technology, we developed a unique analytical setup that is able to simulate hypervelocity ice grains' impact in the laboratory (at speeds in the range of 15-18 km/s) with an unprecedented high mass resolution of up to 150 000 m/Δm (at m/z 19 for a 500 ms signal duration). The results will be implemented in the LILBID database and will be useful for the calibration and future data interpretation of the Europa Clipper's SUrface Dust Analyzer (SUDA), which will characterize the habitability of Jupiter's icy moon Europa.

13.
Macromol Biosci ; 23(6): e2200576, 2023 06.
Artigo em Inglês | MEDLINE | ID: mdl-36810963

RESUMO

Peptides and proteins are exposed to a variety of interfaces in a physiological environment, such as cell membranes, protein nanoparticles (NPs), or viruses. These interfaces have a significant impact on the interaction, self-assembly, and aggregation mechanisms of biomolecular systems. Peptide self-assembly, particularly amyloid fibril formation, is associated with a wide range of functions; however, there is a link with neurodegenerative diseases, such as Alzheimer's disease. This review highlights how interfaces affect peptide structure and the kinetics of aggregation leading to fibril formation. In nature, many surfaces are nanostructures, such as liposomes, viruses, or synthetic NPs. Once exposed to a biological medium, nanostructures are coated with a corona, which then determines their activity. Both accelerating and inhibiting effects on peptide self-assembly have been observed. When amyloid peptides adsorb to a surface, they typically concentrate locally, which promotes aggregation into insoluble fibrils. Starting from a combined experimental and theoretical approach, models that allow for a better understanding of peptide self-assembly near hard and soft matter interfaces are introduced and reviewed. Research results from recent years are presented and relationships between biological interfaces, such as membranes and viruses, and amyloid fibril formation are proposed.


Assuntos
Doença de Alzheimer , Nanopartículas , Humanos , Amiloide/química , Amiloide/metabolismo , Peptídeos/metabolismo , Doença de Alzheimer/metabolismo , Membrana Celular/metabolismo , Nanopartículas/química , Peptídeos beta-Amiloides/química
14.
Astrobiology ; 23(1): 60-75, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36454287

RESUMO

The reliable identification of biosignatures is key to the search for life elsewhere. On ocean worlds like Enceladus or Europa, this can be achieved by impact ionization mass spectrometers, such as the SUrface Dust Analyzer (SUDA) on board NASA's upcoming Europa Clipper mission. During spacecraft flybys, these instruments can sample ice grains formed from subsurface water and emitted by these moons. Previous laboratory analog experiments have demonstrated that SUDA-type instruments could identify amino acids, fatty acids, and peptides in ice grains and discriminate between their abiotic and biotic origins. Here, we report experiments simulating impact ionization mass spectra of ice grains containing DNA, lipids, and metabolic intermediates extracted from two bacterial cultures: Escherichia coli and Sphingopyxis alaskensis. Salty Enceladan or Europan ocean waters were simulated using matrices with different NaCl concentrations. Characteristic mass spectral signals, such as DNA nucleobases, are clearly identifiable at part-per-million-level concentrations. Mass spectra of all substances exhibit unambiguous biogenic patterns, which in some cases show significant differences between the two bacterial species. Sensitivity to the biosignatures decreases with increasing matrix salinity. The experimental parameters indicate that future impact ionization mass spectrometers will be most sensitive to the investigated biosignatures for ice grain encounter speeds of 4-6 km/s.


Assuntos
Meio Ambiente Extraterreno , Gelo , Meio Ambiente Extraterreno/química , Exobiologia , Bactérias , Lipídeos
15.
Data Brief ; 45: 108598, 2022 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-36425960

RESUMO

Nanostructured surfaces are widespread in nature and are being further developed in materials science. This makes them highly relevant for biomolecules, such as peptides. In this data article, we present a curvature model and molecular dynamics (MD) simulation data on the influence of nanoparticle size on the stability of amyloid peptide fibrils related to our research article entitled "Mechanistic insights into the size-dependent effects of nanoparticles on inhibiting and accelerating amyloid fibril formation" (John et al., 2022) [1]. We provide the code to perform MD simulations in GROMACS 4.5.7 software of arbitrarily chosen biomolecule oligomers adsorbed on a curved surface of chosen nanoparticle size. We also provide the simulation parameters and data for peptide oligomers of Aß40, NNFGAIL, GNNQQNY, and VQIYVK. The data provided allows researchers to further analyze our MD simulations and the curvature model allows for a better understanding of oligomeric structures on surfaces.

16.
Materials (Basel) ; 15(13)2022 Jun 24.
Artigo em Inglês | MEDLINE | ID: mdl-35806592

RESUMO

In the study the influence of different dental technical tools on the surface temperature and phase composition of fixed dental prostheses (FDPs) made of yttria-partially stabilized zirconia polycrystals (3Y-/4Y-/5Y-PSZ) was investigated. FDPs were fabricated by using computer-aided manufacturing (CAM). The FDPs were treated with a contra-angle handpiece equipped with different burs and polishers. The resulting surface temperatures were measured with a thermographic camera, and the resulting phase transformations were investigated by X-ray diffraction and quantified by Rietveld refinement. Processing with burs resulted in no phase transformation, but a preferred orientation shift. Using coarse polisher induced a phase transformation to the rhombohedral phase, while fine polishers produced no relevant phase transformations and no preferred orientation shift. Compared to the monoclinic phase (ca. 9% theoretical volume increase), which is associated with low-temperature degradation (LTD), the rhombohedral phase is much more voluminous (ca. 15% theoretical volume increase) and distorted and, therefore, has a greater degradation potential.

17.
J Colloid Interface Sci ; 622: 804-818, 2022 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-35569410

RESUMO

The aggregation of peptides into amyloid fibrils has been linked to ageing-related diseases, such as Alzheimer's and type 2 diabetes. Interfaces, particularly those with large nanostructured surfaces, can affect the kinetics of peptide aggregation, which ranges from complete inhibition to strong acceleration. While a number of physiochemical parameters determine interfacial effects, we focus here on the role of nanoparticle (NP) size and curvature. We used thioflavin T (ThT) fluorescence assays to demonstrate the size-dependent effects of NPs on amyloid fibril formation for the peptides Aß40, NNFGAIL, GNNQQNY and VQIYVK. While 5 nm gold NPs (AuNP-5) retarded or inhibited the aggregation of all peptides except NNFGAIL, larger 20 nm gold NPs (AuNP-20) tended to accelerate or not influence peptide aggregation. Differences in the NP effects for the peptides resulted from the different peptide properties (size, tendency to aggregate) and associated surface binding affinities. Additional dynamic light scattering (DLS), electron microscopy, and atomic force microscopy (AFM) experiments with the Aß40 peptide confirmed size-dependent NP effects on peptide aggregation, and also suggested a structural influence on the formed fibrils. NPs can serve as a surface for the adsorption of peptide monomers and enable nucleation to oligomers and fibril formation. However, molecular dynamics (MD) simulations showed that peptide oligomers were less stable at smaller NPs. High surface curvatures destabilized prefibrillar structures, which provides a possible explanation for inhibitory effects on fibril growth, provided that peptide-NP surface binding was relevant for fibril formation. These mechanistic insights can support the design of future nanostructured materials.


Assuntos
Diabetes Mellitus Tipo 2 , Nanopartículas Metálicas , Nanopartículas , Amiloide/química , Peptídeos beta-Amiloides/química , Ouro , Humanos , Fragmentos de Peptídeos/química
18.
J Phys Chem A ; 126(21): 3373-3383, 2022 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-35579333

RESUMO

An experimental setup for molecular beam scattering from flat liquid sheets has been developed, with the goal of studying reactions at gas-liquid interfaces for volatile liquids. Specifically, a crossed molecular beam instrument that can measure angular and translational energy distributions of scattered products has been adapted for liquid jet scattering. A microfluidic chip is used to create a stable flat liquid sheet inside vacuum from which scattering occurs, and both evaporation and scattering from this sheet are characterized using a rotatable mass spectrometer that can measure product time-of-flight distributions. This article describes the instrument and reports on the first measurements of evaporation of dodecane and Ne from a Ne-doped dodecane flat jet, as well as scattering of Ne from a flat jet of pure dodecane.

19.
Angew Chem Int Ed Engl ; 61(16): e202117855, 2022 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-35088489

RESUMO

Exotic oxidation states of the first-row transition metals have recently attracted much interest. In order to investigate the oxidation states of a series of iron-oxalate complexes, an aqueous solution of iron(III) nitrate and oxalic acid was studied by infrared free liquid matrix-assisted laser desorption/ionization as well as ionspray mass spectrometry. Here, we show that iron is not only detected in its common oxidation states +II and +III, but also in its unusual oxidation state +I, detectable in both positive-ion and in negative-ion modes, respectively. Vibrational spectra of the gas phase anionic iron oxalate complexes [FeIII (C2 O4 )2 ]- , [FeII (C2 O4 )CO2 ]- , and [FeI (C2 O4 )]- were measured by means of infrared photodissociation spectroscopy and their structures were assigned by comparison to anharmonic vibrational spectra based on second-order perturbation theory.

20.
Front Chem ; 10: 1094981, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36700077

RESUMO

Gelatin-based hydrogels are highly desirable biomaterials for use in wound dressing, drug delivery, and extracellular matrix components due to their biocompatibility and biodegradability. However, insufficient and uncontrollable mechanical properties and degradation are the major obstacles to their application in medical materials. Herein, we present a simple but efficient strategy for a novel hydrogel by incorporating the synthetic hydrogel monomer polyethylene glycol diacrylate (PEGDA, offering high mechanical stability) into a biological hydrogel compound (gelatin) to provide stable mechanical properties and biocompatibility at the resulting hybrid hydrogel. In the present work, PEGDA/gelatin hybrid hydrogels were prepared by electron irradiation as a reagent-free crosslinking technology and without using chemical crosslinkers, which carry the risk of releasing toxic byproducts into the material. The viscoelasticity, swelling behavior, thermal stability, and molecular structure of synthesized hybrid hydrogels of different compound ratios and irradiation doses were investigated. Compared with the pure gelatin hydrogel, 21/9 wt./wt. % PEGDA/gelatin hydrogels at 6 kGy exhibited approximately up to 1078% higher storage modulus than a pure gelatin hydrogel, and furthermore, it turned out that the mechanical stability increased with increasing irradiation dose. The chemical structure of the hybrid hydrogels was analyzed by Fourier-transform infrared (FTIR) spectroscopy, and it was confirmed that both compounds, PEGDA and gelatin, were equally present. Scanning electron microscopy images of the samples showed fracture patterns that confirmed the findings of viscoelasticity increasing with gelatin concentration. Infrared microspectroscopy images showed that gelatin and PEGDA polymer fractions were homogeneously mixed and a uniform hybrid material was obtained after electron beam synthesis. In short, this study demonstrates that both the presence of PEGDA improved the material properties of PEGDA/gelatin hybrid hydrogels and the resulting properties are fine-tuned by varying the irradiation dose and PEGDA/gelatin concentration.

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