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Microplastics have been detected in diverse environments, including soil, snowcapped mountains, and even within human organs and blood. These findings have sparked extensive research into the health implications of microplastics for living organisms. Recent studies have shown that microplastics can adsorb onto lipid membranes and induce mechanical stress. In controlled laboratory conditions, the behavior and effects of microplastics can differ markedly from those in natural environments. In this study, we investigate how exposure of microplastics to pollutants affects their interactions with lipid bilayers. Our findings reveal that pollutants, such as chemical solvents, significantly enhance the mechanical stretching effects of microplastics. This suggests that microplastics can act as vectors for harmful pollutants, facilitating their penetration through lipid membranes and thus strongly affect their biophysical properties. This research underscores the complex interplay between microplastics and environmental contaminants.
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The advancements in the capabilities of artificial sensory technologies, such as electronic/optical noses and tongues, have significantly enhanced their ability to identify complex mixtures of analytes. These improvements are rooted in the evolving manufacturing processes of cross-reactive sensor arrays (CRSAs) and the development of innovative computational methods. The potential applications in early diagnosis, food quality control, environmental monitoring, and more, position CRSAs as an exciting area of research for scientists from diverse backgrounds. Among these, plasmonic CRSAs are particularly noteworthy because they offer enhanced capabilities for remote, fast, and even real-time monitoring, in addition to better portability of instrumentation. Specifically, the synergy between the localized surface plasmon resonance (LSPR) of metallic nanoparticles (NPs) and CRSAs introduces advanced techniques such as LSPR, metal-enhanced fluorescence (MEF), surface-enhanced infrared absorption (SEIRA), surface-enhanced Raman scattering (SERS), and surface-enhanced resonance Raman scattering (SERRS) spectroscopies. This review delves into the importance and versatility of optical-CRSAs, especially those based on plasmonic materials, discussing recent applications and potential new research directions.
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Imaging tools are crucial for studying the vascular network and its barrier function in various physiopathological conditions. Shortwave infrared (SWIR) window optical imaging allows noninvasive, in-depth exploration. We applied SWIR imaging, combined with vessel segmentation and deep learning analyses, to study real-time dextran probe extravasation in mice experiencing intermittent hypoxia (IH)-a characteristic of obstructive sleep apnea associated with potential cardiovascular alterations due to early vascular permeability. Evidence for permeability in this context is limited, making our investigation significant. C57Bl/6 mice were exposed to normoxia or intermittent hypoxia for 14 days. Then SWIR imaging between 1,250 and 1,700 nm was performed on the saphenous artery and vein and on the surrounding tissue after intravenous injection of labeled dextrans of two different sizes (10 or 70 kDa). Postprocessing and segmentation of the SWIR images were conducted using deep learning treatment. We monitored high-resolution signals, distinguishing arteries, veins, and surrounding tissues. In the saphenous artery and vein, after 70-kD dextran injection, tissue/vessel ratio was higher after intermittent hypoxia (IH) than normoxia (N) over 500 seconds (P < 0.05). However, the ratio was similar in N and IH after 10-kD dextran injection. The SWIR imaging technique allows noninvasive, real-time monitoring of dextran extravasation in vivo. Dextran 70 extravasation is increased after exposure to IH, suggesting an increased vessel permeability in this mice model of obstructive sleep apnea.NEW & NOTEWORTHY We demonstrate that SWIR imaging technique is a useful tool to monitor real-time dextran extravasation from vessels in vivo, with a high resolution. We report for the first time an increased real-time dextran (70 kD) extravasation in mice exposed to intermittent hypoxia for 14 days compared with normoxic controls.
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Dextranos , Apneia Obstrutiva do Sono , Animais , Camundongos , Hipóxia , Artérias , Camundongos Endogâmicos C57BLRESUMO
This paper presents a comprehensive experimental and theoretical investigation into the antiviral properties of nanostructured surfaces and explains the underlying virucidal mechanism. We used reactive ion etching to fabricate silicon (Si) surfaces featuring an array of sharp nanospikes with an approximate tip diameter of 2 nm and a height of 290 nm. The nanospike surfaces exhibited a 1.5 log reduction in infectivity of human parainfluenza virus type 3 (hPIV-3) after 6 h, a substantially enhanced efficiency, compared to that of smooth Si. Theoretical modeling of the virus-nanospike interactions determined the virucidal action of the nanostructured substrata to be associated with the ability of the sharp nanofeatures to effectively penetrate the viral envelope, resulting in the loss of viral infectivity. Our research highlights the significance of the potential application of nanostructured surfaces in combating the spread of viruses and bacteria. Notably, our study provides valuable insights into the design and optimization of antiviral surfaces with a particular emphasis on the crucial role played by sharp nanofeatures in maximizing their effectiveness.
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Nanoestruturas , Infecções por Paramyxoviridae , Humanos , Silício , Vírus da Parainfluenza 3 Humana , AntiviraisRESUMO
Lateral diffusion of nano-objects on lipid membranes is a crucial process in cell biology. Recent studies indicate that nanoparticle lateral diffusion is affected by the presence of membrane proteins and deviates from Brownian motion. Gold nanoparticles (Au NPs) stabilized by short thiol ligands were dispersed near a free-standing bilayer formed in a 3D microfluidic chip. Using dark-field microscopy, the position of single NPs at the bilayer surface was tracked over time. Numerical analysis of the NP trajectories shows that NP diffusion on the bilayer surface corresponds to Brownian motion. The addition of bovine serum albumin (BSA) protein to the solution led to the formation of a protein corona on the NP surface. We found that protein-coated NPs show anomalous superdiffusion and that the distribution of their relative displacement obeys Lévy flight statistics. This superdiffusive motion is attributed to a drastic reduction in adhesive energies between the NPs and the bilayer in the presence of the protein corona. This hypothesis was confirmed by numerical simulations mimicking the random walk of a single particle near a weakly adhesive surface. These results may be generalized to other classes of nano-objects that experience adsorption-desorption behaviour with a weakly adhesive surface.
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Nanopartículas Metálicas , Nanopartículas , Coroa de Proteína , Ouro , Bicamadas Lipídicas , Proteínas de Membrana , Nanopartículas/metabolismo , Soroalbumina Bovina , Compostos de SulfidrilaRESUMO
Design problems of finding efficient patterns, adaptation of complex molecules to external environments, affinity of molecules to specific targets, dynamic adaptive behavior of chemical systems, reconstruction of 3D structures from diffraction data are examples of difficult to solve optimal design or inverse search problems. Nature inspires evolution strategies to solve design problems that are based on selection of successful adaptations and heritable traits over generations. To exploit this strategy in the creation of new materials, a concept of adaptive chemistry was proposed to provide a route for synthesis of self-adapting molecules that can fit to their environment. We propose a computational method of an efficient exhaustive search exploiting massive parallelization on modern GPUs, which finds a solution for an inverse problem by solving repetitively a direct problem in the mean field approximation. One example is the search for a composition of a copolymer that allows the polymer to translocate through a lipid membrane at a minimal time. Another example is a search of a copolymer sequence that maximizes the polymer load in the micelle defined by the radial core-shell potentials. The length and the composition of the sequence are adjusted to fit into the restricted environment. Hydrogen bonding is another pathway of adaptation to the environment through reversible links. A linear polymer that interacts with water through hydrogen bonds adjusts the position of hydrogen bonds along the chain as a function of the concentration field around monomers. In the last example, branching of the molecules is adjusted to external fields, providing molecules with annealed topology, that can be flexibly changed by changing external conditions. The method can be generalized and applied to a broad spectrum of design problems in chemistry and physics, where adaptive behavior in multi-parameter space in response to environmental conditions lead to non-trivial patterns or molecule architectures and compositions. It can further be combined with machine learning or other optimization techniques to explore more efficiently the parameter space.
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Aprendizado de Máquina , Física , Ligação de Hidrogênio , PolímerosRESUMO
Ultrasmall metal nanoclusters (NCs) are employed in an array of diagnostic and therapeutic applications due to their tunable photoluminescence, high biocompatibility, polyvalent effect, ease of modification, and photothermal stability. However, gold nanoclusters' (AuNCs') intrinsically antimicrobial properties remain poorly explored and are not well understood. Here, we share an insight into the antimicrobial action of atomically precise AuNCs based on their ability to passively translocate across the bacterial membrane. Functionalized by a hydrophilic modified-bidentate sulfobetaine zwitterionic molecule (AuNC-ZwBuEt) or a more hydrophobic monodentate-thiolate, mercaptohexanoic acid (AuNC-MHA) molecule, 2 nm AuNCs were lethal to both Gram-negative Pseudomonas aeruginosa and Gram-positive Staphylococcus aureus bacteria. The bactericidal efficiency was found to be bacterial strain-, time-, and concentration-dependent. The direct visualizations of the translocation of AuNCs and AuNC-cell and subcellular interactions were investigated using cryo-soft X-ray nano-tomography, transmission electron microscopy (TEM), and scanning TEM energy-dispersive spectroscopy analyses. AuNC-MHA were identified in the bacterial cytoplasm within 30 min, without evidence of the loss of membrane integrity. It is proposed that the bactericidal effect of AuNCs is attributed to their size, which allows for efficient energy-independent translocation across the cell membrane. The internalization of both AuNCs caused massive internal damage to the cells, including collapsed subcellular structures and altered cell morphology, leading to the eventual loss of cellular integrity.
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Anti-Infecciosos , Nanopartículas Metálicas , Antibacterianos/farmacologia , Bactérias , Ouro/química , Ouro/farmacologia , Nanopartículas Metálicas/química , Pseudomonas aeruginosa , Staphylococcus aureusRESUMO
The influence of solvent polarity and surface ligand rigidification on the SWIR emission profile of gold nanoclusters with an anistropic surface was investigated. A strong enhancement of the SWIR emission band at 1200 nm was observed when measuring in different local environments: in solution, in polymer composites, and in solids. SWIR in vivo imaging of mice assisted by deep learning after intravenous administration of these gold nanoclusters provides high definition pseudo-3D views of vascular blood vessels.
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Ouro/química , Nanopartículas Metálicas/química , Imagem Molecular/métodos , Animais , Ligantes , Camundongos , Espectrofotometria Infravermelho/métodos , Propriedades de SuperfícieRESUMO
Estimated millions of tons of plastic are dumped annually into oceans. Plastic has been produced only for 70 y, but the exponential rise of mass production leads to its widespread proliferation in all environments. As a consequence of their large abundance globally, microplastics are also found in many living organisms including humans. While the health impact of digested microplastics on living organisms is debatable, we reveal a physical mechanism of mechanical stretching of model cell lipid membranes induced by adsorbed micrometer-sized microplastic particles most commonly found in oceans. Combining experimental and theoretical approaches, we demonstrate that microplastic particles adsorbed on lipid membranes considerably increase membrane tension even at low particle concentrations. Each particle adsorbed at the membrane consumes surface area that is proportional to the contact area between particle and the membrane. Although lipid membranes are liquid and able to accommodate mechanical stress, the relaxation time is much slower than the rate of adsorption; thus, the cumulative effect from arriving microplastic particles to the membrane leads to the global reduction of the membrane area and increase of membrane tension. This, in turn, leads to a strong reduction of membrane lifetime. The effect of mechanical stretching of microplastics on living cells membranes was demonstrated by using the aspiration micropipette technique on red blood cells. The described mechanical stretching mechanism on lipid bilayers may provide better understanding of the impact of microplastic particles in living systems.
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Lipídeos/química , Fenômenos Mecânicos , Membranas Artificiais , Microplásticos/química , Tamanho da Partícula , Polietileno/química , Polimetil Metacrilato/química , Poliestirenos/químicaRESUMO
The impact of protein corona on the interactions of nanoparticles (NPs) with cells remains an open question. This question is particularly relevant to NPs which sizes, ranging from tens to hundreds nanometers, are comparable to the sizes of most abundant proteins in plasma. Protein sizes match with typical thickness of various coatings and ligands layers, usually present at the surfaces of larger NPs. Such size match may affect the properties and the designed function of NPs. We offer a direct demonstration of how protein corona can dramatically change the interaction mode between NPs and lipid bilayers. To this end, we choose the most extreme case of NP surface modification: nanostructures in the form of rigid spikes of 10-20 nm length at the surface of gold nanoparticles. In the absence of proteins we observe the formation of reversible pores when spiky NPs adsorb on lipid bilayers. In contrast, the presence of bovine serum albumin (BSA) proteins adsorbed at the surface of spiked NPs, effectively reduces the length of spikes exposed to the interaction with lipid bilayers. Thus, protein corona changes qualitatively the dynamics of pore formation, which is completely suppressed at high protein concentrations. These results suggest that protein corona can not only be critical for interaction of NPs with membranes, it may change their mode of interaction, thus offsetting the role of surface chemistry and ligands.
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Nanopartículas Metálicas , Nanopartículas , Coroa de Proteína , Ouro , Bicamadas Lipídicas , Soroalbumina BovinaRESUMO
HYPOTHESIS: The ability exhibited by insect wings to resist microbial infestation is a unique feature developed over 400 million years of evolution in response to lifestyle and environmental pressures. The self-cleaning and antimicrobial properties of insect wings may be attributed to the unique combination of nanoscale structures found on the wing surface. EXPERIMENTS: In this study, we characterised the wetting characteristics of superhydrophobic damselfly Calopteryx haemorrhoidalis wings. We revealed the details of air entrapment at the micro- and nano scales on damselfly wing surfaces using a combination of spectroscopic and electron microscopic techniques. Cryo-focused-ion-beam scanning electron microscopy was used to directly observe fungal spores and conidia that were unable to cross the air-liquid interface. By contrast, bacterial cells were able to cross the air-water interface to be ruptured upon attachment to the nanopillar surface. The robustness of the air entrapment, and thus the wing antifungal behaviour, was demonstrated after 1-week of water immersion. A newly developed wetting model confirmed the strict Cassie-Baxter wetting regime when damselfly wings are immersed in water. FINDINGS: We provide evidence that the surface nanopillar topography serves to resist both fungal and bacterial attachment via a dual action: repulsion of fungal conidia while simultaneously killing bacterial cells upon direct contact. These findings will play an important role in guiding the fabrication of biomimetic, anti-fouling surfaces that exhibit both bactericidal and anti-fungal properties.
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Antifúngicos , Odonatos , Animais , Antibacterianos/farmacologia , Molhabilidade , Asas de AnimaisRESUMO
Shortwave infrared window (SWIR: 1000-1700 nm) represents a major improvement compared to the NIR-I region (700-900 nm) in terms of temporal and spatial resolutions in depths down to 4 mm. SWIR is a fast and cheap alternative to more precise methods such as X-ray and opto-acoustic imaging. Main obstacles in SWIR imaging are the noise and scattering from tissues and skin that reduce the precision of the method. We demonstrate that the combination of SWIR in vivo imaging in the NIR-IIb region (1500-1700 nm) with advanced deep learning image analysis allows to overcome these obstacles and making a large step forward to high resolution imaging: it allows to precisely segment vessels from tissues and noise, provides morphological structure of the vessels network, with learned pseudo-3D shape, their relative position, dynamic information of blood vascularization in depth in small animals and distinguish the vessels types: artieries and veins. For demonstration we use neural network IterNet that exploits structural redundancy of the blood vessels, which provides a useful analysis tool for raw SWIR images.
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Aprendizado Profundo , Animais , Raios Infravermelhos , Redes Neurais de Computação , Ondas de RádioRESUMO
Antibiotic resistance is a global human health threat, causing routine treatments of bacterial infections to become increasingly difficult. The problem is exacerbated by biofilm formation by bacterial pathogens on the surfaces of indwelling medical and dental devices that facilitate high levels of tolerance to antibiotics. The development of new antibacterial nanostructured surfaces shows excellent prospects for application in medicine as next-generation biomaterials. The physico-mechanical interactions between these nanostructured surfaces and bacteria lead to bacterial killing or prevention of bacterial attachment and subsequent biofilm formation, and thus are promising in circumventing bacterial infections. This Review explores the impact of surface roughness on the nanoscale in preventing bacterial colonization of synthetic materials and categorizes the different mechanisms by which various surface nanopatterns exert the necessary physico-mechanical forces on the bacterial cell membrane that will ultimately result in cell death.
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Antibacterianos/farmacologia , Infecções Bacterianas/microbiologia , Fenômenos Fisiológicos Bacterianos , Biofilmes/efeitos dos fármacos , Fenômenos Mecânicos , Nanoestruturas , Aderência Bacteriana , Infecções Bacterianas/tratamento farmacológico , Biofilmes/crescimento & desenvolvimento , Membrana Celular/ultraestrutura , Humanos , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Propriedades de SuperfícieRESUMO
It is commonly accepted that nanoparticles (NPs) can kill bacteria; however, the mechanism of antimicrobial action remains obscure for large NPs that cannot translocate the bacterial cell wall. It is demonstrated that the increase in membrane tension caused by the adsorption of NPs is responsible for mechanical deformation, leading to cell rupture and death. A biophysical model of the NP-membrane interactions is presented which suggests that adsorbed NPs cause membrane stretching and squeezing. This general phenomenon is demonstrated experimentally using both model membranes and Pseudomonas aeruginosa and Staphylococcus aureus, representing Gram-positive and Gram-negative bacteria. Hydrophilic and hydrophobic quasi-spherical and star-shaped gold (Au)NPs are synthesized to explore the antibacterial mechanism of non-translocating AuNPs. Direct observation of nanoparticle-induced membrane tension and squeezing is demonstrated using a custom-designed microfluidic device, which relieves contraction of the model membrane surface area and eventual lipid bilayer collapse. Quasi-spherical nanoparticles exhibit a greater bactericidal action due to a higher interactive affinity, resulting in greater membrane stretching and rupturing, corroborating the theoretical model. Electron microscopy techniques are used to characterize the NP-bacterial-membrane interactions. This combination of experimental and theoretical results confirm the proposed mechanism of membrane-tension-induced (mechanical) killing of bacterial cells by non-translocating NPs.
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Antibacterianos/química , Antibacterianos/farmacologia , Membrana Celular/efeitos dos fármacos , Ouro/química , Ouro/farmacologia , Fenômenos Mecânicos/efeitos dos fármacos , Nanopartículas Metálicas , Fenômenos Biomecânicos/efeitos dos fármacos , Membrana Celular/metabolismo , Pseudomonas aeruginosa/citologia , Pseudomonas aeruginosa/efeitos dos fármacos , Staphylococcus aureus/citologia , Staphylococcus aureus/efeitos dos fármacosRESUMO
The mechano-bactericidal activity of nanostructured surfaces has become the focus of intensive research toward the development of a new generation of antibacterial surfaces, particularly in the current era of emerging antibiotic resistance. This work demonstrates the effects of an incremental increase of nanopillar height on nanostructure-induced bacterial cell death. We propose that the mechanical lysis of bacterial cells can be influenced by the degree of elasticity and clustering of highly ordered silicon nanopillar arrays. Herein, silicon nanopillar arrays with diameter 35 nm, periodicity 90 nm and increasing heights of 220, 360, and 420 nm were fabricated using deep UV immersion lithography. Nanoarrays of 360-nm-height pillars exhibited the highest degree of bactericidal activity toward both Gram stain-negative Pseudomonas aeruginosa and Gram stain-positive Staphylococcus aureus bacteria, inducing 95 ± 5% and 83 ± 12% cell death, respectively. At heights of 360 nm, increased nanopillar elasticity contributes to the onset of pillar deformation in response to bacterial adhesion to the surface. Theoretical analyses of pillar elasticity confirm that deflection, deformation force, and mechanical energies are more significant for the substrata possessing more flexible pillars. Increased storage and release of mechanical energy may explain the enhanced bactericidal action of these nanopillar arrays toward bacterial cells contacting the surface; however, with further increase of nanopillar height (420 nm), the forces (and tensions) can be partially compensated by irreversible interpillar adhesion that reduces their bactericidal effect. These findings can be used to inform the design of next-generation mechano-responsive surfaces with tuneable bactericidal characteristics for antimicrobial surface technologies.
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Antibacterianos/farmacologia , Nanoestruturas/química , Estresse Mecânico , Antibacterianos/química , Aderência Bacteriana , Elasticidade , Pseudomonas aeruginosa/efeitos dos fármacos , Pseudomonas aeruginosa/fisiologia , Silício/química , Staphylococcus aureus/efeitos dos fármacos , Staphylococcus aureus/fisiologiaRESUMO
Cholesterol is a crucial component of mammalian cell membranes that takes part in many vital processes. It is generally accepted that cholesterol stabilizes the membrane and induces transitions into ordered states. In contrast to expectations, we demonstrate that cholesterol can destabilize the membrane by creating a nanodomain around a perpendicularly embedded ultrashort carbon nanotube (CNT), and we show that cholesterol triggers the translocation of an ultrashort CNT through the cell membrane. Using atomistic simulations, we report the existence of a nanoscale domain around an ultrashort carbon nanotube within a crossover distance of 0.9 nm from the surface of the nanotube, where the properties of the bilayer are different from the bulk: the domain is characterized by increased fluctuations, increased thickness, and increased order of the lipids with respect to the bulk. Cholesterol decreases the thickness and order of lipids and increases the fluctuations with respect to a pure lipid bilayer. Experimentally, we confirm that cholesterol nanodomains provoke spontaneous translocation of nanotubes through a lipid bilayer even for low membrane tensions. A specially designed microfluidic device allows us to trace the kinetic pathway of the translocation process and establish the threshold cholesterol concentration of 20% for translocation. The reported nanoscale cholesterol-induced membrane restructuring near the ultrashort CNT in lipid membranes enables precise control and specific targeting of a membrane using cholesterol. As an example, it may allow for specific targeting between cholesterol-rich mammalian cells and cholesterol-poor bacterial cells.
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Membrana Celular/química , Colesterol/química , Lipídeos de Membrana/química , Modelos Químicos , Nanotubos de Carbono/química , Membrana Celular/metabolismo , Colesterol/metabolismo , Bicamadas Lipídicas/química , Bicamadas Lipídicas/metabolismo , Lipídeos de Membrana/metabolismo , Modelos BiológicosRESUMO
HYPOTHESIS: Titanium and titanium alloys are often the most popular choice of material for the manufacture of medical implants; however, they remain susceptible to the risk of device-related infection caused by the presence of pathogenic bacteria. Hydrothermal etching of titanium surfaces, to produce random nanosheet topologies, has shown remarkable ability to inactivate pathogenic bacteria via a physical mechanism. We expect that systematic tuning of the nanosheet morphology by controlling fabrication parameters, such as etching time, will allow for optimisation of the surface pattern for superior antibacterial efficacy. EXPERIMENTS: Using time-dependent hydrothermal processing of bulk titanium, we fabricated bactericidal nanosheets with variable nanoedge morphologies according to a function of etching time. A systematic study was performed to compare the bactericidal efficiency of nanostructured titanium surfaces produced at 0.5, 1, 2, 3, 4, 5, 6, 24 and 60â¯h of hydrothermal etching. FINDINGS: Titanium surfaces hydrothermally treated for a period of 6â¯h were found to achieve maximal antibacterial efficiency of 99⯱â¯3% against Gram-negative Pseudomonas aeruginosa and 90⯱â¯9% against Gram-positive Staphylococcus aureus bacteria, two common human pathogens. These surfaces exhibited nanosheets with sharp edges of approximately 10â¯nm. The nanotopographies presented in this work exhibit the most efficient mechano-bactericidal activity against both Gram-negative and Gram-positive bacteria of any nanostructured titanium topography reported thus far.
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Antibacterianos/farmacologia , Temperatura Alta , Nanoestruturas/administração & dosagem , Infecções Estafilocócicas/prevenção & controle , Staphylococcus aureus/efeitos dos fármacos , Titânio/farmacologia , Ligas , Antibacterianos/química , Aderência Bacteriana , Humanos , Nanoestruturas/química , Infecções Estafilocócicas/microbiologia , Staphylococcus aureus/crescimento & desenvolvimento , Propriedades de Superfície , Titânio/químicaRESUMO
Recent technological advances have allowed the development of a new generation of nanostructured materials, such as those displaying both mechano-bactericidal activity and substrata that favor the growth of mammalian cells. Nanomaterials that come into contact with biological media such as blood first interact with proteins, hence understanding the process of adsorption of proteins onto these surfaces is highly important. The Random Sequential Adsorption (RSA) model for protein adsorption on flat surfaces was modified to account for nanostructured surfaces. Phenomena related to the nanofeature geometry have been revealed during the modelling process; e.g., convex geometries can lead to lower steric hindrance between particles, and hence higher degrees of surface coverage per unit area. These properties become more pronounced when a decrease in the size mismatch between the proteins and the surface nanostructures occurs. This model has been used to analyse the adsorption of human serum albumin (HSA) on a nano-structured black silicon (bSi) surface. This allowed the Blocking Function (the rate of adsorption) to be evaluated. The probability of the protein to adsorb as a function of the occupancy was also calculated.
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Nanoestruturas/química , Albumina Sérica/química , Silício/química , Adsorção , Animais , Humanos , Estereoisomerismo , Propriedades de SuperfícieRESUMO
Macromolecules of amphiphilic invertible polymers (AIPs) are capable of self-assembly into micellar assemblies of various morphologies in solvents of different polarities. The micellar assemblies in aqueous media are capable of encapsulating poorly aqueous soluble cargo and can undergo inverse conformational change and cargo release in contact with non-polar media, including potentially, cell membranes. Thus, invertible micellar assemblies have significant potential in drug delivery and related domains. However, to date there have been few investigations into their interactions with lipid membranes. Herein, we investigate the interactions of three recently developed AIPs of varying hydrophobicity/hydrophilicity balance with a highly fluidic microcavity supported 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) lipid bilayer. We combined electrochemical impedance spectroscopy (EIS) with fluorescence correlation spectroscopy (FCS) to understand how the AIP micellar assemblies impacted bilayer permeability and fluidity respectively, across polymer concentrations above and below their critical micelle concentrations (cmcs). At concentration as above their cmcs, all of the AIPs explored increased permeability and decreased the fluidity of the lipid membrane. The extent of impact depended on the hydrophobicity of the AIP. PEG600-PTHF650, the most hydrophobic of the polymers, synthesized from PEG (molecular weight 600â¯g/mol) and PTHF (molecular weight 650â¯g/mol) exerted the greatest influence on the bilayer's physical properties and fluorescence imaging and correlation data indicate that PEG600-PTHF650 micelles loaded with BODIPY probes adsorb and invert at the lipid membrane with release of cargo into the bilayer. This study should help inform future advancement of AIPs for membrane molecular delivery.
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Butileno Glicóis/química , Bicamadas Lipídicas/química , Polietilenoglicóis/química , Polímeros/química , Espectroscopia Dielétrica , Difusão , Corantes Fluorescentes/química , Interações Hidrofóbicas e Hidrofílicas , Micelas , Conformação Molecular , Permeabilidade , Fosfatidilcolinas/química , Solventes/química , Espectrometria de FluorescênciaRESUMO
The waxy epicuticle of dragonfly wings contains a unique nanostructured pattern that exhibits bactericidal properties. In light of emerging concerns of antibiotic resistance, these mechano-bactericidal surfaces represent a particularly novel solution by which bacterial colonization and the formation of biofilms on biomedical devices can be prevented. Pathogenic bacterial biofilms on medical implant surfaces cause a significant number of human deaths every year. The proposed mechanism of bactericidal activity is through mechanical cell rupture; however, this is not yet well understood and has not been well characterized. In this study, we used giant unilamellar vesicles (GUVs) as a simplified cell membrane model to investigate the nature of their interaction with the surface of the wings of two dragonfly species, Austrothemis nigrescens and Trithemis annulata, sourced from Victoria, Australia, and the Baix Ebre and Terra Alta regions of Catalonia, Spain. Confocal laser scanning microscopy and cryo-scanning electron microscopy techniques were used to visualize the interactions between the GUVs and the wing surfaces. When exposed to both natural and gold-coated wing surfaces, the GUVs were adsorbed on the surface, exhibiting significant deformation, in the process of membrane rupture. Differences between the tensile rupture limit of GUVs composed of 1,2-dioleoyl- sn-glycero-3-phosphocholine and the isotropic tension generated from the internal osmotic pressure were used to indirectly determine the membrane tensions, generated by the nanostructures present on the wing surfaces. These were estimated as being in excess of 6.8 mN m-1, the first experimental estimate of such mechano-bactericidal surfaces. This simple model provides a convenient bottom-up approach toward understanding and characterizing the bactericidal properties of nanostructured surfaces.