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[This corrects the article DOI: 10.1371/journal.pone.0281703.].
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Interest in the technique of low temperature environmental nanoindentation has gained momentum in recent years. Low temperature indentation apparatuses can, for instance, be used for systematic measurements of the mechanical properties of ice in the laboratory, in order to accurately determine the inputs for the constitutive equations describing the rheologic behaviour of natural ice (i.e., the Glen flow law). These properties are essential to predict the movement of glaciers and ice sheets over time as a response to a changing climate. Herein, we introduce a new experimental setup and protocol for electron microscope loading and in situ nanoindentation of water ice. Preliminary testing on pure water ice yield elastic modulus and hardness measurements of 4.1 GPa and 176 MPa, respectively, which fall within the range of previously published values. Our approach demonstrates the potential of low temperature, in situ, instrumented nanoindentation of ice under controlled conditions in the SEM, opening the possibility for investigating individual structural elements and systematic studies across species and concentration of impurities to refine to constitutive equations for natural ice.
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Electrones , Agua , Temperatura , Módulo de Elasticidad , DurezaRESUMEN
Interstitials, e.g., C, N, and O, are attractive alloying elements as small atoms on interstitial sites create strong lattice distortions and hence substantially strengthen metals. However, brittle ceramics such as oxides and carbides usually form, instead of solid solutions, when the interstitial content exceeds a critical yet low value (e.g., 2 at.%). Here we introduce a class of massive interstitial solid solution (MISS) alloys by using a highly distorted substitutional host lattice, which enables solution of massive amounts of interstitials as an additional principal element class, without forming ceramic phases. For a TiNbZr-O-C-N MISS model system, the content of interstitial O reaches 12 at.%, with no oxides formed. The alloy reveals an ultrahigh compressive yield strength of 4.2 GPa, approaching the theoretical limit, and large deformability (65% strain) at ambient temperature, without localized shear deformation. The MISS concept thus offers a new avenue in the development of metallic materials with excellent mechanical properties.
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The effect of extracellular polymeric substances (EPS) on the meso-scale physical structure and hydraulic resistance of membrane biofilms during gravity driven membrane (GDM) filtration was investigated. Biofilms were developed on the surface of ultrafiltration membranes during dead-end filtration at ultra-low pressure (70â¯mbar). Biofilm EPS composition (total protein, polysaccharide and eDNA) was manipulated by growing biofilms under contrasting nutrient conditions. Nutrient conditions consisted of (i) a nutrient enriched condition with a nutrient ratio of 100:30:10 (C: N: P), (ii) a phosphorus limitation (C: N: P ratio: 100:30:0), and (iii) a nitrogen limitation (C: N: P ratio: 100:0:10). The structure of the biofilm was characterised at meso-scale using Optical Coherence Tomography (OCT). Biofilm composition was analysed with respect to total organic carbon, total cellular mass and extracellular concentrations of proteins, polysaccharides, and eDNA. 2D-confocal Raman mapping was used to characterise the functional group composition and micro-scale distribution of the biofilms EPS. Our study reveals that the composition of the EPS matrix can determine the meso-scale physical structure of membrane biofilms and in turn its hydraulic resistance. Biofilms grown under P limiting conditions were characterised by dense and homogeneous physical structures with high concentrations of polysaccharides and eDNA. Biofilm grown under nutrient enriched or N limiting conditions were characterised by heterogeneous physical structures with lower concentrations of polysaccharides and eDNA. For P limiting biofilms, 2D-confocal Raman microscopy revealed a homogeneous spatial distribution of anionic functional groups in homogeneous biofilm structures with higher polysaccharide and eDNA concentrations. This study links EPS composition, physical structure and hydraulic resistance of membrane biofilms, with practical relevance for the hydraulic performances of GDM ultrafiltration.
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Biopelículas , Biopolímeros/química , Membranas Artificiales , Ultrafiltración/instrumentación , Biopelículas/crecimiento & desarrollo , Incrustaciones Biológicas , Carbono/metabolismo , ADN/análisis , ADN/química , Matriz Extracelular/metabolismo , Microscopía Confocal , Nitrógeno/metabolismo , Polisacáridos/análisis , Polisacáridos/química , Proteínas/análisis , Proteínas/química , Tomografía de Coherencia ÓpticaRESUMEN
Direct writing utilizing a focused electron beam constitutes an interesting alternative to resist-based techniques, as it allows for precise and flexible growth onto any conductive substrate in a single-step process. One important challenge, however, is the identification of appropriate precursors which allow for deposition of the material of choice, e.g., for envisaged applications in nano-optics. In this regard the coinage metal silver is of particular interest since it shows a relatively high plasma frequency and, thus, excellent plasmonic properties in the visible range. By utilizing the precursor compound AgO2Me2Bu, direct writing of silver-based nanostructures via local electron beam induced deposition could be realized for the first time. Interestingly, the silver deposition was strongly dependent on electron dose; at low doses of 30 nC/µm2 a dominant formation of pure silver crystals was observed, while at higher electron doses around 104 nC/µm2 large carbon contents were measured. A scheme for the enhanced silver deposition under low electron fluxes by an electronic activation of precursor dissociation below thermal CVD temperature is proposed and validated using material characterization techniques. Finally, the knowledge gained was employed to fabricate well-defined two-dimensional deposits with maximized silver content approaching 75 at. %, which was achieved by proper adjustment of the deposition parameters. The corresponding deposits consist of plasmonically active silver crystallites and demonstrate a pronounced Raman signal enhancement of the carbonaceous matrix.
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An effective postgrowth electrical tuning, via an oxygen releasing method, to enhance the content of non-noble metals in deposits directly written with gas-assisted focused-electron-beam-induced deposition (FEBID) is presented. It represents a novel and reproducible method for improving the electrical transport properties of Co-C deposits. The metal content and electrical properties of Co-C-O nanodeposits obtained by electron-induced dissociation of volatile Co2(CO)8 precursor adsorbate molecules were reproducibly tuned by applying postgrowth annealing processes at 100 °C, 200 °C, and 300 °C under high-vacuum for 10 min. Advanced thin film EDX analysis showed that during the annealing process predominantly oxygen is released from the Co-C-O deposits, yielding an atomic ratio of Co:C:O = 100:16:1 (85:14:1) with respect to the atomic composition of as-written Co:C:O = 100:21:28 (67:14:19). In-depth Raman analysis suggests that the amorphous carbon contained in the as-written deposit turns into graphite nanocrystals with size of about 22.4 nm with annealing temperature. Remarkably, these microstructural changes allow for tuning of the electrical resistivity of the deposits over 3 orders of magnitude from 26 mΩ cm down to 26 µΩ cm, achieving a residual resistivity of ρ2K/ρ300 K = 0.56, close to the value of 0.53 for pure Co films with similar dimensions, making it especially interesting and advantageous over the numerous works already published for applications such as advanced scanning-probe systems, magnetic memory, storage, and ferroelectric tunnel junction memristors, as the graphitic matrix protects the cobalt from being oxidized under an ambient atmosphere.
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The micromechanical fracture behavior of Si [100] was investigated as a function of temperature in the scanning electron microscope with a nanoindenter. A gradual increase in KC was observed with temperature, in contrast to sharp transitions reported earlier for macro-Si. A transition in cracking mechanism via crack branching occurs at â¼300 °C accompanied by multiple load drops. This reveals that onset of small-scale plasticity plays an important role in the brittle-to-ductile transition of miniaturized Si.
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The growing incidence of skeletal fractures poses a significant challenge to ageing societies. Since a major part of physiological loading in the lower limbs is carried by cortical bone, it would be desirable to better understand the structure-mechanical property relationships and scale effects in this tissue. This study aimed at assessing whether microindentation properties combined with chemical and morphological information are usable to predict macroscopic elastic and strength properties in a donor- and site-matched manner. Specimens for quasi-static macroscopic tests in tension, compression, and torsion and microindentation were prepared from a cohort of 19 male and 20 female donors (46 to 99 years). All tests were performed under fully hydrated conditions. The chemical composition of the extra-cellular matrix was investigated with Raman spectroscopy. The results of the micro-mechanical tests were combined with morphological and compositional properties using a power law relationship to predict the macro-mechanical results. Microindentation properties were not gender dependent, remarkably constant over age, and showed an overall small variation with standard deviations of approximately 10 %. Similar results were obtained for chemical tissue composition. Macro-mechanical stiffness and strength were significantly related to porosity for all load cases (p<0.05). In case of macroscopic yield strain and work-to-failure this was only true in torsion and compression, respectively. The correlations of macro-mechanical with micro-mechanical, morphological, and chemical properties showed no significance for cement line density, mineralisation, or variations in the microindentation results and were dominated by porosity with a moderate explanatory power of predominately less than 50 %. The results confirm that age, with minor exceptions gender, and small variations in average mineralisation have negligible effect on the tissue microindentation properties of human lamellar bone in the elderly. Furthermore, our findings suggest that microindentation experiments are suitable to predict macroscopic mechanical properties in the elderly only on average and not on a one to one basis. The presented data may help to form a better understanding of the mechanisms of ageing in bone tissue and of the length scale at which they are active. This may be used for future prediction of fracture risk in the elderly.
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Hueso Cortical/fisiología , Factores de Edad , Anciano , Anciano de 80 o más Años , Fenómenos Biomecánicos , Estudios de Cohortes , Femenino , Humanos , Masculino , Persona de Mediana Edad , Porosidad , Espectrometría Raman , Donantes de Tejidos , Microtomografía por Rayos XRESUMEN
Super-soft PEG hydrogel particles with tunable elasticity are prepared via a mesoporous silica templating method. The deformability behavior of these particles, in a microfluidic blood-capillary model, can be tailored to be similar to that of human red blood cells. These results provide a new platform for the design and development of soft hydrogel particles for investigating bio-nano interactions.
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Materiales Biomiméticos/química , Elasticidad , Hidrogeles/química , Polietilenglicoles/química , Capilares/fisiología , Simulación por Computador , Módulo de Elasticidad , Eritrocitos/fisiología , Análisis de Elementos Finitos , Humanos , Microfluídica/métodos , Microscopía de Fuerza Atómica , Microscopía Electrónica de Rastreo , Microscopía Electrónica de Transmisión , Microscopía Fluorescente , Modelos Biológicos , Soluciones , Agua/químicaRESUMEN
Hybrid and multicompartment carriers are of significant interest for the development of next-generation therapeutic drug carriers. Herein, fundamental investigations on layer-by-layer (LbL) capsules consisting of two different polymers are presented. The hybrid systems were designed to have pH-responsive, charge-shifting poly(2-(diisopropylamino)ethyl methacrylate) (PDPA) inner layers and low-fouling poly(N-vinylpyrrolidone) (PVPON) outer layers. Planar hybrid films with different layer ratios were studied by quartz crystal microgravimetry (QCM) and atomic force microscopy (AFM). The information obtained was translated to particulate templates to prepare hybrid capsules, which were stabilized by click chemistry. The charge-shifting behavior of PDPA improved the cargo encapsulation and initial retention of a model CpG cargo, while outer layers of PVPON improved biofouling properties compared to single-component PDPA capsules. The results demonstrate the need to understand and design multifunctional systems that can successfully embody different functionalities in a single, stable construct for the fabrication of next-generation drug and gene delivery carriers aimed at overcoming the challenges encountered in biological systems.
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Portadores de Fármacos/química , Ácidos Polimetacrílicos/química , Povidona/química , Incrustaciones Biológicas , Cápsulas , Química Clic , Unión Proteica , Pirrolidinonas , Propiedades de SuperficieRESUMEN
The mechanical properties of the shell of ultrasonically synthesized lysozyme microbubbles, LSMBs, were evaluated by acoustic interrogation and nanoindentation techniques. The Young's modulus of LSMBs was found to be 1.0 ± 0.3 MPa and 0.6 ± 0.1 MPa when analyzed by flow cytometry and AFM, respectively. The shell elasticity and Young's modulus were not affected by the size of the microbubbles (MBs). The hydrogel-like protein shell of LSMBs offers a softer, more elastic and viscous interface compared to lipid-shelled MBs. We show that the acoustic interrogation technique is a real-time, fast, and high-throughput method to characterize the mechanical characteristics of air-filled microbubbles coated by a variety of materials.
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Fenómenos Mecánicos , Microburbujas , Muramidasa , Elasticidad , Citometría de Flujo , Microscopía de Fuerza Atómica , Muramidasa/química , Muramidasa/ultraestructura , UltrasonidoRESUMEN
Faceted polymer microcapsules are prepared from metal-organic framework (MOF) templates. The MOF templates are removable under mild aqueous conditions. The obtained microcapsules are stiffer than their spherical counterparts, reflecting the near-incompressibility of the facet edges, and indicating that the faceting might be a useful strategy for controlling the mechanical properties of polymer microcapsules.
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Soft hydrogel particles with tunable mechanical properties are promising for next-generation therapeutic applications. This is due to the increasingly proven role that physicochemical properties play in particulate-based delivery vectors, both in vitro and in vivo. The ability to understand and quantify the mechanical properties of such systems is therefore essential to optimize function and performance. We report control over the mechanical properties of poly(methacrylic acid) (PMA) hydrogel particles based on a mesoporous silica templating method. The mechanical properties of the obtained particles can be finely tuned through variation of the cross-linker concentration, which is hereby quantified using a cross-linking polymer with a fluorescent tag. We demonstrate that the mechanical properties of the particles can be elucidated using an atomic force microscopy (AFM) force spectroscopy method, which additionally allows for the study of hydrogel material properties at the nanoscale through high-resolution force mapping. Young's modulus and stiffness of the particles were tuned between 0.04 and 2.53 MPa and between 1.6 and 28.4 mN m(-1), respectively, through control over the cross-linker concentration. The relationship between the concentration of the cross-linker added and the amount of adsorbed polymer was observed to follow a Langmuir isotherm, and this relationship was found to correlate linearly with the particle mechanical properties.
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Reactivos de Enlaces Cruzados/química , Hidrogel de Polietilenoglicol-Dimetacrilato/química , Nanoestructuras/química , Ácidos Polimetacrílicos/química , Reactivos de Enlaces Cruzados/síntesis química , Tamaño de la Partícula , Porosidad , Propiedades de SuperficieRESUMEN
While soft hydrogel nano- and microstructures hold great potential for therapeutic treatments and in vivo applications, their nanomechanical characterization remains a challenge. In this paper, soft, single-component, supported hydrogel films were fabricated using pendant-thiol-modified poly(methacrylic acid) (PMASH). The influence of hydrogel architecture on deformation properties was studied by fabricating films on particle supports and producing free-standing capsules. The influence of the degree of thiol-based cross-linking on the mechanical properties of the soft hydrogel systems (core-shell and capsules) was studied using a colloidal-probe (CP) AFM technique. It was found that film mechanical properties, stability, and capsule swelling could be finely tuned by controlling the extent of poly(methacrylic acid) thiol modification. Furthermore, switching the pH from 7.4 to 4.0 led to film densification due to increased hydrogen bonding. Hydrogel capsule systems were found to have stiffness values ranging from 0.9 to 16.9 mN m(-1) over a thiol modification range of 5 to 20 mol %. These values are significantly greater than those for previously reported PMASH planar films of 0.7-5.7 mN m(-1) over the same thiol modification range (Best et al., Soft Matter 2013, 9, 4580-4584). Films on particle substrates had comparable mechanical properties to planar films, demonstrating that while substrate geometry has a negligible effect, membrane and tension effects may play an important role in capsule force resistance. Further, when transitioning from solid-supported films to free-standing capsules, simple predictions of shell stiffness based on modulus changes found for supported films are not valid. Rather, additional effects like diameter increases (geometrical changes) as well as tension buildup need to be taken into account. These results are important for research related to the characterization of soft hydrogel materials and control over their mechanical properties.
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Hidrogel de Polietilenoglicol-Dimetacrilato/química , Cápsulas/química , Concentración de Iones de Hidrógeno , Estructura Molecular , Tamaño de la Partícula , Ácidos Polimetacrílicos/química , Compuestos de Sulfhidrilo/química , Propiedades de SuperficieRESUMEN
The development of facile and versatile strategies for thin-film and particle engineering is of immense scientific interest. However, few methods can conformally coat substrates of different composition, size, shape, and structure. We report the one-step coating of various interfaces using coordination complexes of natural polyphenols and Fe(III) ions. Film formation is initiated by the adsorption of the polyphenol and directed by pH-dependent, multivalent coordination bonding. Aqueous deposition is performed on a range of planar as well as inorganic, organic, and biological particle templates, demonstrating an extremely rapid technique for producing structurally diverse, thin films and capsules that can disassemble. The ease, low cost, and scalability of the assembly process, combined with pH responsiveness and negligible cytotoxicity, makes these films potential candidates for biomedical and environmental applications.
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Ingeniería Química/métodos , Complejos de Coordinación/síntesis química , Polifenoles/química , Taninos/química , Cápsulas/química , Cápsulas/toxicidad , Complejos de Coordinación/toxicidad , Compuestos Férricos/química , Compuestos Férricos/toxicidad , Concentración de Iones de Hidrógeno , Polifenoles/toxicidad , Propiedades de Superficie , Taninos/toxicidadRESUMEN
DNA-loaded polypeptide particles are prepared via templated assembly of mesoporous silica for the delivery of adjuvants. The elasticity and cargo-loading capacity of the obtained particles can be tuned by the amount of cross-linker used to stabilize the polypeptide particles. The use of polypeptide particles as biocarriers provides a promising method for vaccine delivery.
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Adyuvantes Inmunológicos/metabolismo , Adyuvantes Inmunológicos/farmacología , Fenómenos Mecánicos , Nanotecnología , Péptidos/metabolismo , Ingeniería de Proteínas , Adyuvantes Inmunológicos/química , Secuencia de Bases , Islas de CpG , Células Dendríticas/efectos de los fármacos , Células Dendríticas/inmunología , Portadores de Fármacos/metabolismo , Humanos , Oligonucleótidos/química , Oligonucleótidos/genética , Oligonucleótidos/metabolismo , Ácido Poliglutámico/químicaRESUMEN
Nanostructured particulate materials are expected to revolutionize diagnostics and the delivery of therapeutics for healthcare. To date, chemistry-derived solutions have been the major focus in the design of materials to control interactions with biological systems. Only recently has control over a new set of physical parameters, including size, shape, and rigidity, been explored to optimize the biological response and the in vivo performance of nanoengineered delivery vectors. This Review highlights the methods used to manipulate the physical properties of particles and the relevance of these physical properties to cellular and circulatory interactions. Finally, the importance of future work to synergistically tailor both physical and chemical properties of particulate materials is discussed, with the aim of improving control over particle interactions in the biological domain.
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Materiales Biocompatibles/química , Nanopartículas/química , Nanopartículas/ultraestructura , Conformación Molecular , Tamaño de la Partícula , Propiedades de SuperficieRESUMEN
Nanoengineered particles that can facilitate drug formulation and passively target tumors have reached the clinic in recent years. These early successes have driven a new wave of significant innovation in the generation of advanced particles. Recent developments in enabling technologies and chemistries have led to control over key particle properties, including surface functionality, size, shape, and rigidity. Combining these advances with the rapid developments in the discovery of many disease-related characteristics now offers new opportunities for improving particle specificity for targeted therapy. In this Perspective, we summarize recent progress in particle-based therapeutic delivery and discuss important concepts in particle design and biological barriers for developing the next generation of particles.