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In this paper, we demonstrate the infrared photoluminescence emission from Ge(Si) quantum dots coupled with collective Mie modes of silicon nanopillars. We show that the excitation of band edge dipolar modes of a linear nanopillar array results in strong reshaping of the photoluminescence spectra. Among other collective modes, the magnetic dipolar mode with the polarization along the array axis contributes the most to the emission spectrum, exhibiting an experimentally measured Q-factor of around 500 for an array of 11 pillars. The results belong to the first experimental evidence of light emission enhancement of quantum emitters applying collective Mie resonances in finite nanoresonators and therefore represent an important contribution to the new field of active all-dielectric meta-optics.
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Transition-metal phosphides (TMP) prepared by atomic layer deposition (ALD) are reported for the first time. Ultrathin Co-P films were deposited by using PH3 plasma as the phosphorus source and an extra H2 plasma step to remove excess P in the growing films. The optimized ALD process proceeded by self-limited layer-by-layer growth, and the deposited Co-P films were highly pure and smooth. The Co-P films deposited via ALD exhibited better electrochemical and photoelectrochemical hydrogen evolution reaction (HER) activities than similar Co-P films prepared by the traditional post-phosphorization method. Moreover, the deposition of ultrathin Co-P films on periodic trenches was demonstrated, which highlights the broad and promising potential application of this ALD process for a conformal coating of TMP films on complex three-dimensional (3D) architectures.
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Resonant dielectric nanostructures represent a promising platform for light manipulation at the nanoscale. In this paper, we describe an active photonic system based on Ge(Si) quantum dots coupled to silicon nanodisks. We show that Mie resonances govern the enhancement of the photoluminescent signal from embedded quantum dots due to a good spatial overlap of the emitter position with the electric field of Mie modes. We identify the coupling mechanism, which allows for engineering the resonant Mie modes through the interaction of several nanodisks. In particular, the mode hybridization in a nanodisk trimer results in an up to 10-fold enhancement of the luminescent signal due to the excitation of resonant antisymmetric magnetic and electric dipole modes.
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Intrinsic cross-linking is not only useful for increasing stability, but also for tailoring mechanical properties of polyelectrolyte multilayers (PEM) on implants and tissue engineering scaffolds. Here, a novel route for synthesizing thiolated chitosan (t-Chi) based on the application of 3,3'-dithiodipropionic acid was applied, while thiolated chondroitin sulfate (t-CS) was conjugated by 3,3'-dithiobis (propanoic hydrazide). Both products were subsequently reduced to obtain the free thiols. The thiol content, structural changes and degree of substitution were studied by UV-vis, FTIR, Raman and 1H NMR spectroscopy, respectively. Chi and CS can be used for PEM formation with the layer-by-layer method, due to the cationic nature of Chi at pH values below 5.0 and the anionic character of CS. Comparative studies on the formation of native Chi/CS versus t-Chi/t-CS PEM with surface plasmon resonance and ellipsometry revealed higher layer mass. We also found that the PEM composed of t-Chi/t-CS had superior cell adhesion properties for human keratinocytes in comparison to the native PEM.
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Adhesión Celular , Quitosano/química , Queratinocitos/citología , Polielectrolitos/química , Andamios del Tejido , Células Cultivadas , HumanosRESUMEN
Skin aging is characterized by different features including wrinkling, atrophy of the dermis and loss of elasticity associated with damage to the extracellular matrix protein elastin. The aim of this study was to investigate the aging process of skin elastin at the molecular level by evaluating the influence of intrinsic (chronological aging) and extrinsic factors (sun exposure) on the morphology and susceptibility of elastin towards enzymatic degradation. Elastin was isolated from biopsies derived from sun-protected or sun-exposed skin of differently aged individuals. The morphology of the elastin fibers was characterized by scanning electron microscopy. Mass spectrometric analysis and label-free quantification allowed identifying differences in the cleavage patterns of the elastin samples after enzymatic digestion. Principal component analysis and hierarchical cluster analysis were used to visualize differences between the samples and to determine the contribution of extrinsic and intrinsic aging to the proteolytic susceptibility of elastin. Moreover, the release of potentially bioactive peptides was studied. Skin aging is associated with the decomposition of elastin fibers, which is more pronounced in sun-exposed tissue. Marker peptides were identified, which showed an age-related increase or decrease in their abundances and provide insights into the progression of the aging process of elastin fibers. Strong age-related cleavage occurs in hydrophobic tropoelastin domains 18, 20, 24 and 26. Photoaging makes the N-terminal and central parts of the tropoelastin molecules more susceptible towards enzymatic cleavage and, hence, accelerates the age-related degradation of elastin.
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Envejecimiento , Elastina/metabolismo , Envejecimiento de la Piel , Piel/metabolismo , Adolescente , Adulto , Anciano , Anciano de 80 o más Años , Secuencia de Aminoácidos , Niño , Elastina/genética , Elastina/ultraestructura , Femenino , Prepucio/metabolismo , Humanos , Masculino , Microscopía Electrónica de Rastreo , Persona de Mediana Edad , Elastasa Pancreática/metabolismo , Péptidos/metabolismo , Análisis de Componente Principal , Piel/efectos de la radiación , Luz Solar , Tropoelastina/genética , Tropoelastina/metabolismo , Adulto JovenRESUMEN
Arrays of differently sized disk shaped gold nanoantennas are prepared on glass, which show localized surface plasmon resonance and Rayleigh anomalies in the near infrared and telecom range between 1000 and 1500 nm wavelength. The spectral position of these grating resonances depends critically on the period of the array and the size of the nanoantennas. When PbS quantum dots embedded in PMMA surround the nanoantennas, an up to four fold enhancement of the photoluminescence is observed at the grating resonances due to the constructive diffractive feedback among neighboring antennas. In accordance with the grating resonances a shift of the emission towards smaller wavelengths with decreasing disk diameter is demonstrated.
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Stability of surface coatings against environmental stress, such as pH, high ionic strength, mechanical forces, and so forth, is crucial for biomedical application of implants. Here, a novel extracellular-matrix-like polyelectrolyte multilayer (PEM) system composed of collagen I (Col I) and oxidized glycosaminoglycans (oGAGs) was stabilized by intrinsic cross-linking due to formation of imine bonds between aldehydes of oxidized chondroitin sulfate (oCS) or hyaluronan (oHA) and amino groups of Col I. It was also found that Col I contributed significantly more to overall mass in CS-Col I than in HA-Col I multilayer systems and fibrillized particularly in the presence of native and oxidized CS. Adhesion and proliferation studies with murine C3H10T1/2 embryonic fibroblasts demonstrated that covalent cross-linking of oGAG with Col I had no adverse effects on cell behavior. By contrast, it was found that cell size and polarization was more pronounced on oGAG-based multilayer systems, which corresponded also to the higher stiffness of cross-linked multilayers as observed by studies with quartz crystal microbalance (QCM). Overall, PEMs prepared from oGAG and Col I give rise to stable PEM constructs due to intrinsic cross-linking that may be useful for making bioactive coatings of implants and tissue engineering scaffolds.
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Colágeno Tipo I/química , Reactivos de Enlaces Cruzados/química , Glicosaminoglicanos/química , Animales , Adhesión Celular/efectos de los fármacos , Adhesión Celular/fisiología , Proliferación Celular/efectos de los fármacos , Proliferación Celular/fisiología , Células Cultivadas , Colágeno Tipo I/farmacología , Reactivos de Enlaces Cruzados/farmacología , Glicosaminoglicanos/farmacología , Ratones , Ratones Endogámicos C3H , Oxidación-Reducción/efectos de los fármacos , Andamios del TejidoRESUMEN
OBJECTIVES: The recently introduced ultrasonic osteotome procedure is an alternative to conventional methods of osteotomy. The aim of the present study was to establish the differences between five recently introduced ultrasonic osteotomes and to perform micromorphological and quantitative roughness analyses of osteotomized bone surfaces. MATERIALS AND METHODS: Fresh, standard-sized bony samples were taken from a rabbit skull using the following ultrasonic osteotomes: the Piezosurgery 3 with insert tip OT7, Piezosurgery Medical with insert tip MT1-10, Piezon Master Surgery with insert tip SL1, VarioSurg with inert tip SG1, and Piezotome 2 with insert tip BS1 II. The required duration of time for each osteotomy was recorded. The prepared surfaces were examined via light microscopy, environmental surface electron microscopy (ESEM), and confocal laser scanning microscopy (CLSM). RESULTS: All of the investigated piezoelectric osteotomes preserved the anatomical structure of bone. The mean roughness values of the osteotomized bone edge obtained using the investigated piezoelectric osteotomes were as follows: 2.47 µm (Piezosurgery 3), 9.79 µm (Piezosurgery Medical), 4.66 µm (Piezon Master Surgery), 6.38 µm (VarioSurg), and 6.06 µm (Piezotome 2). Significantly higher roughness values were observed when using the Piezosurgery Medical in comparison with those achieved by the Piezosurgery 3 (P<0.0001) and Piezon Master Surgery (P=0.002). Different osteotomy durations were achieved using the different piezoelectric osteotomes: 144 s (Piezosurgery 3), 126 s (Piezosurgery Medical), 142 s (Piezon Master Surgery), 149 s (VarioSurg), and 137 s (Piezotome 2). CONCLUSIONS: In the present study, micromorphological differences following the use of various ultrasonic devices were clearly identified. According to this study, it can be concluded that the power and the composition of the teeth of the insert tip might impact procedure duration and cutting qualities.
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Craneotomía/instrumentación , Ultrasonido , Animales , Femenino , Microscopía Confocal , Microscopía Electrónica de Rastreo , Conejos , Estadísticas no Paramétricas , Propiedades de SuperficieRESUMEN
Al(2)O(3) and TiO(2) thin films have been deposited on Si wafers, quartz, BK7 glass, and polycarbonate substrates by atomic layer deposition (ALD). The refractive indices and growth rates of the materials have been determined by spectroscopic ellipsometry and transmission electron microscopy. The influence of substrate temperature and precursor on the refractive indices has been investigated. The refractive index of TiO(2) significantly increases with temperature, whereas the Al(2)O(3) films are temperature insensitive. The films deposited using H(2)O(2) as oxygen source show a slightly higher refractive index than the films prepared with H(2)O. Multilayer narrow-bandpass filters and broadband antireflective coatings have been designed and produced by ALD.
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Measurement of the elastic properties of single osteon lamellae is still one of the most demanding tasks in bone mechanics to be solved. By means of site-matched Raman microspectroscopy, acoustic microscopy and nanoindentation the structure, chemical composition and anisotropic elasticity of individual lamellae in secondary osteons were investigated. Acoustic impedance images (911-MHz) and two-dimensional Raman spectra were acquired in sections of human femoral bone. The samples were prepared with orientations at various observation angles theta relative to the femoral long axis. Nanoindentations provided local estimations of the elastic modulus and landmarks necessary for spatial fusion of the acoustic and spectral Raman images. Phosphate nu(1) (961 cm(-1)) and amide I (1665 cm(-1)) band images representing spatial distributions of mineral and collagen were fused with the acoustic images. Acoustic impedance was correlated with the indentation elastic modulus E(IT) (R(2)=0.61). Both parameters are sensitive to elastic tissue anisotropy. The lowest values were obtained in the direction perpendicular to the femoral long axis. Acoustic images exhibit a characteristic bimodal lamellar pattern of alternating high and low impedance values. Since this undulation was not associated with a variation of the phosphate nu(1)-band intensity in the Raman images, it was attributed to variations of the lamellar orientation. After threshold segmentation and conversion to elastic modulus the orientation and transverse isotropic elastic constants were derived for individual ensembles of apparent thin and thick lamellae. Our results suggest that this model represents the effective anisotropic properties of an asymmetric twisted plywood structure made of transverse isotropic fibrils. This is the first report that proves experimentally the ability of acoustic microscopy to map tissue elasticity in two dimensions with micrometer resolution. The combination with Raman microspectroscopy provides a unique way to study bone and mineral metabolism and the relation with mechanical function at the ultrastructural tissue level.