RESUMEN
We investigate the nanometrology of sub-nanometre particle sizes in industrially manufactured sodium silicate liquors at high pH using time-resolved fluorescence anisotropy. Rather than the previous approach of using a single dye label, we investigate and quantify the advantages and limitations of multiplexing two fluorescent dye labels. Rotational times of the non-binding rhodamine B and adsorbing rhodamine 6G dyes are used to independently determine the medium microviscosity and the silicate particle radius, respectively. The anisotropy measurements were performed on the range of samples prepared by diluting the stock solution of silicate to concentrations ranging between 0.2 M and 2 M of NaOH and on the stock solution at different temperatures. Additionally, it was shown that the particle size can also be measured using a single excitation wavelength when both dyes are present in the sample. The recovered average particle size has an upper limit of 7.0 ± 1.2 Å. The obtained results were further verified using small-angle X-ray scattering, with the recovered particle size equal to 6.50 ± 0.08 Å. To disclose the impact of the dye label on the measured complex size, we further investigated the adsorption state of rhodamine 6G on silica nanoparticles using molecular dynamics simulations, which showed that the size contribution is strongly impacted by the size of the nanoparticle of interest. In the case of the higher radius of curvature (less curved) of larger particles, the size contribution of the dye label is below 10%, while in the case of smaller and more curved particles, the contribution increases significantly, which also suggests that the particles of interest might not be perfectly spherical.
RESUMEN
With the fast development of new science and technology, wearable devices are in great demand in modern human daily life. However, the energy problem is a long-lasting issue to achieve real smart, wearable, and portable devices. Flexible thermoelectric generators (TEGs) based on thermoelectric conversion systems can convert body waste heat into electricity with excellent flexibility and wearability, which shows a new direction to solving this issue. Here in this work, polyethylenimine (PEI) and gold nanoparticles (Au NPs) twin surface-modified carbon nanotube fibers (CNTFs) were designed and prepared to fabricate thermoelectric textiles (TET) with high performance, good air stability, and high-efficiency power generation. To better utilize the heat emitted by the human body, microencapsulated phase change materials (MPCM) were coated on the hot end of the TET to achieve the phase-transition-promoted TET. MPCM-coated TET device could generate 25.7% more energy than the untreated control device, which indicates the great potential of the phase-transition-promoted TET.
RESUMEN
Gold nanorods (GNRs) have emerged as the most efficient photothermal agent in cancer therapy and photocatalysis. Understanding the influence of the surrounding medium, particle size, and excitation wavelength is critical to optimising the photothermal conversion rate. Here, three pairs of large and small gold nanorods of different aspect ratios and their heat generation under laser radiation at on and off surface plasmon resonance wavelengths in aqueous solution and gel-like media are investigated. In the aqueous solution, the temperature rise of the large gold nanorods is more than with small gold nanorods at resonance excitation. In contrast to the large gold nanorods (LGNRs), the small gold nanorods (SGNRs) were less sensitive to excitation wavelength. At off-resonance excitation, the temperature rise of the SGNRs is larger than that of the LGNRs. In the agarose gel, the photothermal effect of the SGNRs is greater than LGNRs excited at the wavelength near their solution phase longitudinal surface plasmon resonance wavelength. The temperature increase of LGNRs in gel is significantly less than in aqueous solution. These findings suggest that SGNRs could be more beneficial than the LGNRs for photothermal applications in biological systems and provides further insight when selecting GNRs.
Asunto(s)
Oro , Nanotubos , Tamaño de la Partícula , Resonancia por Plasmón de Superficie/métodos , TemperaturaRESUMEN
We have studied the evolution of keratin intrinsic fluorescence as an indicator of its glycation. Steady-state and time-resolved fluorescence of free keratin and keratin-glucose samples were detected in PBS solutionsin vitro. The changes in the fluorescence response demonstrate that the effect of glucose is manifest in the accelerated formation of fluorescent cross-links with an emission peak at 460 nm and formation of new cross-links with emission peaks at 525 nm and 575 nm. The fluorescence kinetics of these structures is studied and their potential application for the detection of long-term complications of diabetes discussed.
Asunto(s)
Queratinas , Reacción de Maillard , Fluorescencia , Glucosa/químicaRESUMEN
We report the effects of quercetin, a flavonoid present in the human diet, on early stage beta-amyloid (Aß) aggregation, a seminal event in Alzheimer's disease. Molecular level changes in Aß arrangements are monitored by time-resolved emission spectral (TRES) measurements of the fluorescence of Aß's single tyrosine intrinsic fluorophore (Tyr). The results suggest that quercetin binds ß-amyloid oligomers at early stages of their aggregation, which leads to the formation of modified oligomers and hinders the creation of ß-sheet structures, potentially preventing the onset of Alzheimer's disease.
Asunto(s)
Enfermedad de Alzheimer , Péptidos beta-Amiloides , Enfermedad de Alzheimer/metabolismo , Amiloide/química , Péptidos beta-Amiloides/química , Flavonoides/farmacología , Humanos , Fragmentos de Péptidos/química , Quercetina/farmacología , Tirosina/químicaRESUMEN
We report an organophotocatalytic, N-CH3-selective oxidation of trialkylamines in continuous flow. Based on the 9,10-dicyanoanthracene (DCA) core, a new catalyst (DCAS) was designed with solubilizing groups for flow processing. This allowed O2 to be harnessed as a sustainable oxidant for late-stage photocatalytic N-CH3 oxidations of complex natural products and active pharmaceutical ingredients bearing functional groups not tolerated by previous methods. The organophotocatalytic gas-liquid flow process affords cleaner reactions than in batch mode, in short residence times of 13.5 min and productivities of up to 0.65 g per day. Spectroscopic and computational mechanistic studies showed that catalyst derivatization not only enhanced solubility of the new catalyst compared to poorly-soluble DCA, but profoundly diverted the photocatalytic mechanism from singlet electron transfer (SET) reductive quenching with amines toward energy transfer (EnT) with O2.
RESUMEN
Collagen's long half-life (in skin approximately 10 years) makes this protein highly susceptible to glycation and formation of the advanced glycation end products (AGEs). Accumulation of cross-linking AGEs in the skin collagen has several detrimental effects; thus, the opportunity for non-invasive monitoring of skin glycation is essential, especially for diabetic patients. In this paper, we report using the time-resolved intrinsic fluorescence of collagen as a biomarker of its glycation. Contrary to the traditional fluorescence intensity decay measurement at the arbitrarily selected excitation and detection wavelengths, we conducted systematic wavelength- and time-resolved measurements to achieve time-resolved emission spectra. Changes in the intrinsic fluorescence kinetics, caused by both collagen aggregation and glycation, have been detected.
Asunto(s)
Colágeno , Productos Finales de Glicación Avanzada , Fluorescencia , Humanos , Cinética , PielRESUMEN
Fluorescence guided surgery (FGS) is an imaging technique that allows the surgeon to visualise different structures and types of tissue during a surgical procedure that may not be as visible under white light conditions. Due to the many potential advantages of fluorescence guided surgery compared to more traditional clinical imaging techniques such as its higher contrast and sensitivity, less subjective use, and ease of instrument operation, the research interest in fluorescence guided surgery continues to grow over various key aspects such as fluorescent probe development and surgical system development as well as its potential clinical applications. This review looks to summarise some of the emerging opportunities and developments that have already been made in fluorescence guided surgery in recent years while highlighting its advantages as well as limitations that need to be overcome in order to utilise the full potential of fluorescence within the surgical environment.
Asunto(s)
Colorantes Fluorescentes , FluorescenciaRESUMEN
We monitor early stages of beta-amyloid (Aß1-40) aggregation, one of the key processes leading to Alzheimer's disease (AD), in the presence of high glucose concentrations by measuring Aß1- 40 intrinsic fluorescence. The multiple peaks and their shifts observed in the time-resolved emission spectra (TRES) reveal the impact of glycation on Aß1- 40 oligomerisation. The results show that formation of the advanced glycation end products (AGEs) alters the aggregation pathway. These changes are highly relevant to our understanding of the pathophysiology of AD and the implication of AGE and diabetes in these pathways.
Asunto(s)
Enfermedad de Alzheimer/metabolismo , Péptidos beta-Amiloides/química , Diabetes Mellitus/metabolismo , Fragmentos de Péptidos/química , Multimerización de Proteína , Péptidos beta-Amiloides/metabolismo , Humanos , Fragmentos de Péptidos/metabolismoRESUMEN
We performed time-resolved transient absorption and fluorescence anisotropy measurements in order to study tautomerization of porphycene in rigid polymer matrices at cryogenic temperatures. Studies were carried out in poly(methyl methacrylate) (PMMA), poly(vinyl butyral) (PVB), and poly(vinyl alcohol) (PVA). The results prove that in all studied media hydrogen tunnelling plays a significant role in the double hydrogen transfer which becomes very sensitive to properties of the environment below approx. 150 K. We also demonstrate that there exist two populations of porphycene molecules in rigid media: "hydrogen-transferring" molecules, in which tautomerization occurs on time scales below 1 ns and "frozen" molecules in which double hydrogen transfer is too slow to be monitored with nanosecond techniques. The number of "frozen" molecules increases when the sample is cooled. We explain this effect by interactions of guest molecules with a rigid host matrix which disturbs symmetry of porphycene and hinders tunnelling. Temperature dependence of the number of hydrogen-transferring molecules suggests that the factor which restores the symmetry of the double-minimum potential well in porphycene are intermolecular vibrations localized in separated regions of the amorphous polymer.
RESUMEN
Extracellular vesicles (EVs) have numerous potential applications in the field of healthcare and diagnostics, and research into their biological functions is rapidly increasing. Mainly because of their small size and heterogeneity, there are significant challenges associated with their analysis and despite overt evidence of the potential of EVs in clinical diagnostic practice, guidelines for analytical procedures have not yet been properly established. Here, we present an overview of the main methods for studying the properties of EVs based on the principles of fluorescence. Setting aside the isolation, purification and physicochemical characterization strategies which answer questions about the size, surface charge and stability of EVs (reviewed elsewhere), we focus on available optical tools that enable the direct analysis of phenotype and mechanisms of interaction with tissues. In brief, the topics on which we elaborate range from the most popular approaches such as nanoparticle tracking analysis and flow cytometry, to less commonly used techniques such as fluorescence depolarization and microarrays as well as emerging areas such as fast fluorescence lifetime imaging microscopy (FLIM). We highlight that understanding the strengths and limitations of each method is essential for choosing the most appropriate combination of analytical tools. Finally, future directions of this rapidly developing area of medical diagnostics are discussed.
RESUMEN
Small gold nanorods have a significantly large absorption/scattering ratio and are especially beneficial in exploiting photothermal effects, for example in photothermal therapy and remote drug release. This work systematically investigates the influence of growth conditions on the size, growth yield, and stability of small gold nanorods. The silver-assisted seed-mediated growth method was optimized to synthesize stable small gold nanorods with a high growth yield (>85%). Further study on the influence of silver ions on the growth facilitates the growth of small gold nanorods with tunable longitudinal surface plasmon resonance from 613 to 912 nm, with average dimensions of 13-25 nm in length and 5-6 nm in diameter. Moreover, the small gold nanorods were successfully functionalized with thiol-modified hairpin oligonucleotides (hpDNA) labeled with Cy5. Fluorescence intensity measurements show an increase in the presence of target DNA and an enhanced signal/background ratio when the longitudinal surface plasmon resonance of small gold nanorods overlaps with the excitation and emission wavelength of Cy5. This coincides with a reduced fluorescence lifetime of Cy5 in the hairpin structure, indicating surface plasmon resonance-enhanced energy transfer to the small gold nanorods. This study may provide insight on the synthesis and functionalization of small gold nanorods in biomedical sensing and therapy.
RESUMEN
A non-invasive intrinsic fluorescence sensing of the early stages of Alzheimer's beta amyloid peptide aggregation in the presence of copper ions is reported. By using time-resolved fluorescence techniques the formation of beta amyloid-copper complexes and the accelerated peptide aggregation are demonstrated. The shifts in the emission spectral peaks indicate that the peptides exhibit different aggregation pathways than in the absence of copper.
Asunto(s)
Péptidos beta-Amiloides/metabolismo , Cobre/química , Espectrometría de Fluorescencia , Tirosina/química , Enfermedad de Alzheimer/metabolismo , Enfermedad de Alzheimer/patología , Péptidos beta-Amiloides/química , Humanos , Iones/químicaRESUMEN
The application of time-resolved fluorescence sensing to the study of heterogenic biomolecular systems remains challenging because of the complexity of the resulting photophysics. Measuring the time-resolved emission spectroscopy (TRES) spectra can provide a more informative alternative to the modeling of the fluorescence decay that is currently employed. Here, we demonstrate this approach by monitoring real-time changes in intrinsic insulin fluorescence by TRES as a straightforward probe to directly measure kinetics of insulin aggregation and glycation. Our findings hold promise for monitoring the storage of insulin and its application in the control of diabetes and may support the development of more effective therapeutics against amyloidosis.
Asunto(s)
Insulina/análogos & derivados , Fluorescencia , Insulina/química , Cinética , Espectrometría de Fluorescencia , Factores de TiempoRESUMEN
Protein aggregation can lead to several incurable amyloidosis diseases. The full aggregation pathway is not fully understood, creating the need for new methods of studying this important biological phenomenon. Lysozyme is an amyloidogenic protein which is often used as a model protein for studying amyloidosis. This work explores the potential of employing Lysozyme encapsulated gold nanoclusters (Ly-AuNCs) to study the protein's aggregation. The fluorescence emission properties of Ly-AuNCs were studied in the presence of increasing concentrations of native lysozyme and as a function of pH, of relevance in macromolecular crowding and inflammation-triggered aggregation. AuNC fluorescence was observed to both redshift and increase in intensity as pH is increased or when native lysozyme is added to a solution of Ly-AuNCs at pHâ¯3. The long (µs) fluorescence lifetime component of AuNC emission was observed to decrease under both conditions. Interestingly it was found via Time-Resolved Emission Spectra (TRES) that both AuNC fluorescence components increase in intensity and redshift with increasing pH while only the long lifetime component of AuNC was observed to change when adding native lysozyme to solution; indicating that the underlying mechanisms for the changes observed are fundamentally different for each case. It is possible that the sensitivity of Ly-AuNCs to native lysozyme concentration could be utilized to study early-stage aggregation.
Asunto(s)
Oro/química , Nanopartículas del Metal/química , Muramidasa/química , Animales , Pollos , Concentración de Iones de Hidrógeno , Muramidasa/metabolismo , Agregado de Proteínas/fisiología , Espectrometría de FluorescenciaRESUMEN
The excited-state kinetics of the fluorescence of tyrosine in a de novo protein fibrillogenesis model was investigated as a potential tool for monitoring protein fibre formation and complexation with glucose (glycation). In stark contrast to insulin the time-resolved emission spectra (TRES) recorded over the period of 700 hours in buffered solutions of the model with and without glucose revealed no apparent changes in Tyr fluorescence responses. This indicates the stability of the model and provides a measurement-supported basis for its use as a reference material in fluorescence studies of protein aggregation.