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Chemical structures bearing a combination of aggregation-induced emission enhancement (AIEE) and intramolecular charge transfer (ICT) properties attracted the attention of many researchers. Recently, there is an increasing demand to pose tunable AIEE and ICT fluorophores that could present their conformation changes-related emission colors by adjusting the medium polarity. In this study, we designed and synthesized a series of 4-alkoxyphenyl-substituted 1,8-naphthalic anhydride derivatives NAxC using the Suzuki coupling reaction to construct donor-acceptor (D-A)-type fluorophores with alkoxyl substituents of varying carbon chain lengths (x = 1, 2, 4, 6, 12 in NAxC). To explain the observation that molecules with longer carbon chains revealed unusual fluorescence enhancement in water, we study the optical properties and evaluate their locally excited (LE) and ICT states by solvent effects combined with Lippert-Mataga plots. Then, we explored the self-assembly abilities of these molecules in water-organic (W/O) mixed solutions and observed the morphology of its nanostructure using a fluorescence microscope and SEM. The results show that NAxC, x = 4, 6, 12 show different degrees of self-assembly behaviors and corresponding aggregation-induced emission enhancement (AIEE) progresses. At the same time, different nanostructures and corresponding spectral changes can be obtained by adjusting the water ratio in the mixed solution. That is, NAxC compounds present different transitions between LE, ICT and AIEE based on the polarity, water ratio and time changes. We designed NAxC as the structure-activity relationship (SAR) of the surfactant to demonstrate that AIEE comes from the formation of micelle-like nanoaggregates, which causes a restriction of the transfer from the LE state to the ICT state, and micelle formation results in a blue-shift in emission and enhances the intensity in the aggregate state. Among them, NA12C is most likely to form micelles and the most obvious fluorescence enhancement, which will switch over time due to the nano-aggregation transition.
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Micelas , Agua , Solventes/química , Espectrometría de FluorescenciaRESUMEN
Vertebral disc degenerative disease (DDD) affects millions of people worldwide and is a critical factor leading to low back and neck pain and consequent disability. Currently, no strategy has addressed curing DDD from fundamental aspects, because the pathological mechanism leading to DDD is still controversial. One possible mechanism points to the homeostatic status of extracellular matrix (ECM) anabolism, and catabolism in the disc may play a vital role in the disease's progression. If the damaged disc receives an abundant amount of cartilage, anabolic factors may stimulate the residual cells in the damaged disc to secrete the ECM and mitigate the degeneration process. To examine this hypothesis, a cartilage anabolic factor, Runx1, was expressed by mRNA through a sophisticated polyamine-based PEG-polyplex nanomicelle delivery system in the damaged disc in a rat model. The mRNA medicine and polyamine carrier have favorable safety characteristics and biocompatibility for regenerative medicine. The endocytosis of mRNA-loaded polyplex nanomicelles in vitro, mRNA delivery efficacy, hydration content, disc shrinkage, and ECM in the disc in vivo were also examined. The data revealed that the mRNA-loaded polyplex nanomicelle was promptly engulfed by cellular late endosome, then spread into the cytosol homogeneously at a rate of less than 20 min post-administration of the mRNA medicine. The mRNA expression persisted for at least 6-days post-injection in vivo. Furthermore, the Runx1 mRNA delivered by polyplex nanomicelles increased hydration content by ≈43% in the punctured disc at 4-weeks post-injection (wpi) compared with naked Runx1 mRNA administration. Meanwhile, the disc space and ECM production were also significantly ameliorated in the polyplex nanomicelle group. This study demonstrated that anabolic factor administration by polyplex nanomicelle-protected mRNA medicine, such as Runx1, plays a key role in alleviating the progress of DDD, which is an imbalance scenario of disc metabolism. This platform could be further developed as a promising strategy applied to regenerative medicine.
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Subunidad alfa 2 del Factor de Unión al Sitio Principal/genética , Técnicas de Transferencia de Gen , Degeneración del Disco Intervertebral/genética , Degeneración del Disco Intervertebral/terapia , Micelas , Sistema de Administración de Fármacos con Nanopartículas , ARN Mensajero/administración & dosificación , Animales , Modelos Animales de Enfermedad , Endocitosis , Expresión Génica , Terapia Genética , Disco Intervertebral/diagnóstico por imagen , Disco Intervertebral/metabolismo , Disco Intervertebral/patología , Degeneración del Disco Intervertebral/diagnóstico por imagen , Degeneración del Disco Intervertebral/patología , Masculino , Imagen Molecular , Nanomedicina , Ratas , Transgenes , Resultado del Tratamiento , Microtomografía por Rayos XRESUMEN
In this manuscript, silver nanowire 3D random crossed-wire woodpile (3D-RCW) nanostructures were designed and prepared. The 3D-RCW provides rich "antenna" and "hot spot" effects that are responsive for surface-enhanced Raman scattering (SERS) effects and plasmon-enhanced fluorescence (PEF). The optimal construction mode for the 3D-RCW, based on the ratio of silver nanowire and control compound R6G, was explored and established for use in PEF and SERS analyses. We found that the RCW nanochip capable of emission and Raman-enhanced detections uses micro levels of analysis volumes. Consequently, and SERS and PEF of pesticides (thiram, carbaryl, paraquat, fipronil) were successfully measured and characterized, and their detection limits were within 5 µM~0.05 µM in 20 µL. We found that the designed 3D plasmon-enhanced platform cannot only collect the SERS of pesticides, but also enhance the fluorescence of a weak emitter (pesticides) by more than 1000-fold via excitation of the surface plasmon resonance, which can be used to extend the range of a fluorescence biosensor. More importantly, solid-state measurement using a 3D-RCW nanoplatform shows promising potential based on its dual applications in creating large SERS and PEF enhancements.
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Fluorescencia , Nanocables/química , Plata/química , Resonancia por Plasmón de Superficie , Espectrometría RamanRESUMEN
The potent DNA-binding compound triaminotriazine-acridine conjugate (Z1) functions by targeting T:T mismatches in CTG trinucleotide repeats that are responsible for causing neurological diseases such as myotonic dystrophy type 1, but its binding mechanism remains unclear. We solved a crystal structure of Z1 in a complex with DNA containing three consecutive CTG repeats with three T:T mismatches. Crystallographic studies revealed that direct intercalation of two Z1 molecules at both ends of the CTG repeat induces thymine base flipping and DNA backbone deformation to form a four-way junction. The core of the complex unexpectedly adopts a U-shaped head-to-head topology to form a crossover of each chain at the junction site. The crossover junction is held together by two stacked G:C pairs at the central core that rotate with respect to each other in an X-shape to form two nonplanar minor-groove-aligned G·C·G·C tetrads. Two stacked G:C pairs on both sides of the center core are involved in the formation of pseudo-continuous duplex DNA. Four metal-mediated base pairs are observed between the N7 atoms of G and CoII, an interaction that strongly preserves the central junction site. Beyond revealing a new type of ligand-induced, four-way junction, these observations enhance our understanding of the specific supramolecular chemistry of Z1 that is essential for the formation of a noncanonical DNA superstructure. The structural features described here serve as a foundation for the design of new sequence-specific ligands targeting mismatches in the repeat-associated structures.
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Acridinas/química , ADN/química , Sustancias Intercalantes/química , Triazinas/química , Disparidad de Par Base , Emparejamiento Base , ADN/genética , Conformación de Ácido Nucleico , Timina/química , Repeticiones de TrinucleótidosRESUMEN
This study proposes to develop a dual-acting antibacterial film of porous chitosan (Cs) embedded with small molecular compound, which possesses photosensitive characteristics with bactericidal efficacy, to promote the accelerated recovery of infectious wounds. The Cs/small molecular compound (Cs-cpd.2) dressing was prepared using the freeze-drying method. Characterization of the synthesized Cs-cpd.2 indicated that it has high porosity and moisture absorption effect, hence enhancing the absorption of wound exudate. Experimental results showed that Cs-cpd.2 dressing has good bactericidal and bacteriostatic effects on Staphylococcus aureus under visible-light irradiation and has antibacterial effect in the dark. It was also found that the small molecular compound does not have cytotoxicity at a dose of 0-5 µM. Furthermore, Cs-cpd.2 that contained small molecular compound with a concentration of 0.3-1 µM has positive effect on both the cell viability rate and cell proliferation rate of human fibroblast CG1639. Cs-cpd.2 can significantly promote cell proliferation when the small molecular compound and the basic fibroblast growth factor bFGF were added together. Therefore, the proposed Cs-cpd.2 dressing is feasible for photodynamic therapy (PDT) and clinical wound dressing applications.
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The major challenge in the fabrication of fluorescent silica nanoparticles (FSNs) based on dye-doped silica nanoparticles (DDSNs) is aggregation-caused fluorescence quenching. Here, we constructed an FSN based on a double emission enhancement (DEE) platform. A thio-reactive fluorescence turn-on molecule, N-butyl-4-(4-maleimidostyryl)-1,8-naphthalimide (CS), was bound to a silane coupling agent, (3-mercaptopropyl)-trimethoxysilane (MPTMS), and the product N-butyl-4-(3-(trimethoxysilyl-propylthio)styryl)-1,8-naphthalimide (CSP) was further used to fabricate a core-shell nanoparticle through the Stöber method. We concluded that the turn-on emission by CSP originated from the photoinduced electron transfer (PET) between the maleimide moiety and the CSP core scaffold, and the second emission enhancement was attributed to the aggregation-induced emission enhancement (AIEE) in CSP when encapsulated inside a core-shell nanoparticle. Thus, FSNs could be obtained through DEE based on a combination of PET and AIEE effects. Systematic investigations verified that the resulting FSNs showed the traditional solvent-independent and photostable optical properties. The results implied that the novel FSNs are suitable as biomarkers in living cells and function as fluorescent visualizing agents for intracellular imaging and drug carriers.
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Diagnóstico por Imagen/métodos , Colorantes Fluorescentes/química , Aumento de la Imagen/métodos , Nanopartículas/química , Espectrometría de Fluorescencia/métodos , Células A549 , Biomarcadores/metabolismo , Línea Celular Tumoral , Portadores de Fármacos/química , Fluorescencia , Células HeLa , Humanos , Naftalimidas/química , Dióxido de Silicio/química , Solventes/químicaRESUMEN
Melanogenesis is a complex physiological mechanism involving various paracrine factors. Skin cells such as keratinocytes, fibroblasts, and melanocytes communicate with one another through secreted regulators, thereby regulating the melanocytes' bio-functions. The stem cell factor (SCF) is a paracrine factor produced by fibroblasts, and its receptor, c-kit, is expressed on melanocytes. Binding of SCF to c-kit activates autophosphorylation and tyrosine kinase to switch on its signal transmission. SCF inhibition does not suppress fibroblast proliferation in MTT assay, and SCF silencing induced mRNA expressions of paracrine factor genes, HGF, NRG-1, and CRH in qPCR results. Following UVB stimulation, gene expressions of HGF, NRG, and CRH were higher than homeostasis; in particular, HGF exhibited the highest correlation with SCF variations. We detected fibroblasts regulated SCF in an autocrine-dependent manner, and the conditioned medium obtained from fibroblast culture was applied to treat melanocytes. Melanogenesis-related genes, tyrosinase and pmel17, were upregulated under conditioned mediums with SCF silencing and exposed to UVB treatments. Melanin quantities in the melanocytes had clearly increased in the pigment content assay. In conclusion, SCF silencing causes variations in both fibroblast paracrine factors and melanocyte melanogenesis, and the differences in gene expressions were observed following UVB exposure.
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Fibroblastos/metabolismo , Silenciador del Gen , Melanocitos/metabolismo , Comunicación Paracrina , Proteínas Proto-Oncogénicas c-kit/genética , Factor de Células Madre/genética , Proliferación Celular , Técnicas de Silenciamiento del Gen , Humanos , Melaninas/biosíntesis , Proteínas Proto-Oncogénicas c-kit/metabolismo , Interferencia de ARN , Factor de Células Madre/metabolismo , Rayos UltravioletaRESUMEN
Tiny bubbles readily stick onto substrates owing to contact angle hysteresis (CAH). Nevertheless, they can slide slowly on a tilted surface with ultralow CAH because capillarity is overcome by buoyancy. It is surprising to observe experimentally that bubbles of 3-15 µL (diameter 1.79-3.06 mm) slide beneath a tilted superhydrophobic surface at a vertical ascent rate faster than that of freely rising ones of high Reynold numbers ≈O(102). As the tilting angle increases, the drag coefficient remains essentially the same as that of a freely rising bubble, but the frontal area of the flat bubble rises monotonically. Nonetheless, the frontal area of the sliding bubble always stays much smaller than that of a freely rising bubble. Consequently, the small drag force associated with the sliding bubbles is attributed to their substantially small frontal areas on superhydrophobic surfaces.
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This manuscript describes the preparation of water soluble aggregation-induced emission enhancement (AIEE)-based fluorescent organic nanoparticles (FONs). The fluorescence diversity of the FONs was investigated in the presence of silver nanowires. We observed that the emission of the FONs can be enhanced by mixing with the nanowires, which is believed to originate from resonance between the emission of the FONs and the surface plasmon resonances of the metal surface. That is, the AIEE phenomenon was promoted according to the metal-enhanced fluorescence (MEF) mechanism that can be used to build up a novel double emission enhancement (DEE) platform and to extend the range of AIEE applications. The systemic fluorescence enhancement, lifetime and photostability were measured and the AIEE-MEF evaluation and the interaction between the FONs and nanowires were discussed based on the obtained spectral data and SEM and fluorescent microscopy images.
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A water-soluble pH sensor, 2-(6-(4-aminostyryl)-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)-N, N-dimethylethanamine (ADA), was synthesized based on the molecular design of photoinduced electron transfer (PET) and intramolecular charge transfer (ICT). The fluorescence emission response against a pH value is in the range 3-6, which is suitable for labelling intracellular pH-dependent microenvironments. After biological evolution, ADA is more than a pH biosensor because it is also an endocytosis pathway tracking biosensor that labels endosomes, late endosomes, and lysosome pH gradients. From this, the emissive aggregates of ADA and protonated-ADA in these organs were evaluated to explore how this probe stresses emission colour change to cause these unique cellular images.
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Colorantes Fluorescentes/química , Imagen Óptica , Orgánulos/química , Células Cultivadas , Colorantes Fluorescentes/síntesis química , Humanos , Concentración de Iones de Hidrógeno , Estructura MolecularRESUMEN
G-quadruplex (G4) is a promising target for anti-cancer treatment. In this paper, we provide the first evidence supporting the presence of G4 in the mitochondrial DNA (mtDNA) of live cells. The molecular engineering of a fluorescent G4 ligand, 3,6-bis(1-methyl-4-vinylpyridinium) carbazole diiodide (BMVC), can change its major cellular localization from the nucleus to the mitochondria in cancer cells, while remaining primarily in the cytoplasm of normal cells. A number of BMVC derivatives with sufficient mitochondrial uptake can induce cancer cell death without damaging normal cells. Fluorescence studies of these anti-cancer agents in live cells and in isolated mitochondria from HeLa cells have demonstrated that their major target is mtDNA. In this study, we use fluorescence lifetime imaging microscopy to verify the existence of mtDNA G4s in live cells. Bioactivity studies indicate that interactions between these anti-cancer agents and mtDNA G4 can suppress mitochondrial gene expression. This work underlines the importance of fluorescence in the monitoring of drug-target interactions in cells and illustrates the emerging development of drugs in which mtDNA G4 is the primary target.
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Antineoplásicos/química , Carbazoles/química , ADN Mitocondrial/química , Colorantes Fluorescentes/química , G-Cuádruplex , Compuestos de Piridinio/química , Animales , Antineoplásicos/toxicidad , Carbazoles/toxicidad , Línea Celular , Células HeLa , Humanos , Ratones Endogámicos BALB C , Microscopía Fluorescente , Compuestos de Piridinio/toxicidadRESUMEN
The microvascular network is a simple but critical system that is responsible for a range of important biological mechanisms in the bodies of all animals. The ability to generate a functional microvessel not only makes it possible to engineer vital tissue of considerable size but also serves as a platform for biomedical studies. However, most of the current methods for generating microvessel networks in vitro use rectangular channels which cannot represent real vessels in vivo and have dead zones at their corners, hence hindering the circulation of culture medium. We propose a scaffold-wrapping method which enables fabrication of a customized microvascular network in vitro in a more biomimetic way. By integrating microelectromechanical techniques with thermal reflow, we designed and fabricated a microscale hemi-cylindrical photoresist template. A replica mold of polydimethylsiloxane, produced by casting, was then used to generate cylindrical scaffolds with biodegradable poly(lactide-co-glycolide) (PLGA). Human umbilical vein endothelial cells were seeded on both sides of the PLGA scaffold and cultured using a traditional approach. The expression of endothelial cell marker CD31 and intercellular junction vascular endothelial cadherin on the cultured cell demonstrated the potential of generating a microvascular network with a degradable cylindrical scaffold. Our method allows cells to be cultured on a scaffold using a conventional culture approach and monitors cell conditions continuously. We hope our cell-covered scaffold can serve as a framework for building large tissues or can be used as the core of a vascular chip for in vitro circulation studies.
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The encounter of a nanodrop with a trench on a hysteresis-free surface is explored by many-body dissipative particle dynamics to show the effect of surface roughness on droplet wetting. A free nanodrop exhibits Brownian motion and the diffusivity decays exponentially with the liquid-solid contact area. In contrast, as the nanodrop sits on a trench, its random motion is constrained. Work must be done to overcome the energy barriers for the transition between free and trapped states. The potential energy landscape is thus constructed based on the force-displacement plot. It is shown that the trench acts as a hydrophobic blemish for capture but like a hydrophilic blemish for escape. A drop always breaks up after detachment from a hydrophilic trench. Therefore, the drop tends to bypass a small trench when it meets one. The macroscopic experiments are performed by fabricating liquid-infused surfaces with extremely low contact angle hysteresis. The experimental observations agree qualitatively with simulation outcomes.
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The self-coating process of solid particles over a liquid drop is important for the formation of a liquid marble. Generally, some external forces such as rolling or flipping are used to cover a drop by small particles. In this work, it is observed that flaky copper powders can spontaneously spread over the planar water surface and form a dense flat cluster with a fractal dimension of 2. Moreover, flaky copper powders can cover the water pendant and sessile drops spontaneously and rapidly. This powder-coated drop can roll on an inclined plane at a relatively high speed. However, spontaneous self-coating disappears for spheroidal copper powders. To explain our observations, the shape factors of particles are introduced into the spreading coefficient S for powders on the liquid surface. The flaky powders have the lowest shape factors and therefore spontaneous self-coating formation, with S > 0.
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The stability of air pockets formed in grooves on a surface is relevant to contact angle hysteresis of droplet wetting and it is investigated by imbibition experiments and surface evolver (SE) simulations. Liquid drops of different wettabilities are placed atop a conical hole on a polymethyl methacrylate (PMMA) substrate. The stability of the air pocket depends on surface wettability. Four kinds of imbibition behaviors ranging from wetting to nonwetting are observed. The imbibition pathway for the kinetically unstable air pocket is observed by using the olive oil droplet. It involves an inward flow of a thin liquid film along the wall of the hole. The accumulation of liquid at the bottom leads to the rise of the air bubble. The energy-barrier profile associated with the imbibition pathway acquired by SE simulations is able to interpret the outcome of imbibition. The advancing and receding contact angles of various liquids on a PMMA substrate with drilled holes are also determined. Their wetting behaviors can be categorized into three types. Our experimental results for substrates with or without fluorination are in good agreement with the theory based on the stability of air pockets.
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A new class of near-infrared (NIR)-absorptive (>900â nm) photosensitizer based on a phenothiazinium scaffold is reported. The stable solid compound, o-DAP, the oxidative form of 3,7-bis(4-methylaminophenyl)-10H-phenothiazine, can generate reactive oxygen species (ROS, singlet oxygen and superoxide) under appropriate irradiation conditions. After biologically evaluating the intracellular uptake, localization, and phototoxicity of this compound, it was concluded that o-DAP is photostable and a potential selective photodynamic therapy (PDT) agent under either NIR or white light irradiation because its photodamage is more efficient in cancer cells than in normal cells and is without significant dark toxicity. This is very rare for photosensitizers in PDT applications.
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Fenotiazinas/síntesis química , Fotoquimioterapia/métodos , Fármacos Fotosensibilizantes/síntesis química , Línea Celular , Fibroblastos/efectos de los fármacos , Fibroblastos/efectos de la radiación , Células HeLa , Humanos , Oxidación-Reducción , Fenotiazinas/química , Fenotiazinas/farmacología , Procesos Fotoquímicos , Fármacos Fotosensibilizantes/química , Fármacos Fotosensibilizantes/farmacología , Especies Reactivas de Oxígeno/química , Oxígeno Singlete/químicaRESUMEN
The nanostructure can collapse due to elasto-capillary interactions. On the basis of free energy analysis for three cases, the contact between double beams can be induced by equilibrium contact or instability. In the former mechanism, the beam contact can be achieved by a gradual increase of deformation with increasing the liquid volume. In the latter mechanism, a sudden rise of deformation occurs due to the divergence of the Laplace pressure as the liquid volume exceeds a critical value. For the case of free-fixed beams, the collapse phase diagram is obtained in the structure aspect ratio-liquid volume plane. The collapse by equilibrium contact occurs for a large aspect ratio but that by instability happens for a small aspect ratio. For the case of fixed-fixed beams, the collapse can occur at the midpoint of two beams by instability.
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The emergence of SARS-CoV-2 variants diminished the efficacy of current antiviral drugs and vaccines. Hence, identifying highly conserved sequences and potentially druggable pockets for drug development was a promising strategy against SARS-CoV-2 variants. In viral infection, the receptor-binding domain (RBD) proteins are essential in binding to the host receptor. Others, Heparan sulfate (HS), widely distributed on the surface of host cells, is thought to play a central role in the viral infection cycle of SARS-CoV-2. Therefore, it might be a reasonable strategy for antiviral drug design to interfere with the RBD in the HS binding site. In this study, we used computational approaches to analyze multiple sequences of coronaviruses and reveal important information about the binding of HS to RBD in the SARS-CoV-2 spike protein. Our results showed that the potential hot-spots, including R454 and E471, in RBD, exhibited strong interactions in the HS-RBD binding region. Therefore, we screened different compounds in the natural product database towards these hot-spots to find potential antiviral candidates using LibDock, Autodock vina and furthermore applying the MD simulation in AMBER20. The results showed three potential natural compounds, including Acetoside (ACE), Hyperoside (HYP), and Isoquercitrin (ISO), had a strong affinity to the RBD. Our results demonstrate a feasible approach to identify potential antiviral agents by evaluating the binding interaction between viral glycoproteins and host receptors. The present study provided the applications of the structure-based computational approach for designing and developing of new antiviral drugs against SARS-CoV-2 variants.
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COVID-19 , SARS-CoV-2 , Glicoproteína de la Espiga del Coronavirus , Humanos , SARS-CoV-2/metabolismo , Antivirales/química , Desarrollo de Medicamentos , Unión Proteica , Sitios de UniónRESUMEN
Lipid droplets (LDs) are spherical organelles that localize in the cytosol of eukaryotic cells. Different proteins are embedded on the surface of LDs, so LDs play a vital role in the physiological activities of cells. The dysregulation of LDs is associated with various human diseases, such as diabetes and obesity. Therefore, it is essential to develop a fluorescent dye that labels LDs to detect and monitor illnesses. In this study, we developed the compound BDAA12C for staining LDs in cells. BDAA12C exhibits excellent LD specificity and low toxicity, enabling us to successfully stain and observe the fusion of LDs in A549 cancer cells. Furthermore, we also successfully distinguished A549 cancer cells and MRC-5 normal cells in a co-culture experiment and in normal and tumour tissues. Interestingly, we found different localizations of BDAA12C in well-fed and starved A549 cancer cells and consequently illustrated the transfer of fatty acids (FAs) from LDs to mitochondria to supply energy for ß-oxidation upon starvation. Therefore, BDAA12C is a promising LD-targeted probe for cancer diagnosis and tracking lipid trafficking within cells.
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Colorantes Fluorescentes , Gotas Lipídicas , Humanos , Gotas Lipídicas/metabolismo , Gotas Lipídicas/química , Colorantes Fluorescentes/química , Células A549 , Neoplasias/diagnóstico por imagen , Neoplasias/metabolismo , Ácidos Grasos/química , Técnicas de Cocultivo , Mitocondrias/metabolismo , Acridinas/química , Microscopía FluorescenteRESUMEN
The liquid drop captured at the capillary end, which is observed in capillary valve and pendant drop technique, is investigated theoretically and experimentally. Because of contact line pinning of the lower meniscus, the lower contact angle is able to rise from the intrinsic contact angle (θ*) so that the external force acting on the drop can be balanced by the capillary force. In the absence of contact angle hysteresis (CAH), the upper contact angle remains at θ*. However, in the presence of CAH, the upper contact angle can descend to provide more capillary force. The coupling between the lower and upper contact angles determines the equilibrium shape of the captured drop. In a capillary valve, the pinned contact line can move across the edge as the pressure difference exceeds the valving pressure, which depends on the geometrical characteristic and wetting property of the valve opening. When CAH is considered, the valving pressure is elevated because the capillary force is enhanced by the receding contact angle. For a pendant drop under gravity, the maximal capillary force is achieved as the lower contact angle reaches 180° in the absence of CAH. However, in the presence of CAH, four regimes can be identified by three critical drop volumes. The lower contact angle can exceed 180°, and therefore the drop takes on the shape of a light bulb, which does not exist in the absence of CAH. The comparisons between Surface Evolver simulations and experiments are quite well.