Controlling the broadband enhanced light chirality with L-shaped dielectric metamaterials.

The inherently weak chiroptical responses of natural materials limit their usage for controlling and enhancing chiral light-matter interactions. Recently, several nanostructures with subwavelength scale dimensions were demonstrated, mainly due to the advent of nanofabrication technologies, as a potential alternative to efficiently enhance chirality. However, the intrinsic lossy nature of metals and the inherent narrowband response of dielectric planar thin films or metasurface structures pose severe limitations toward the practical realization of broadband and tailorable chiral systems. Here, we tackle these problems by designing all-dielectric silicon-based L-shaped optical metamaterials based on tilted nanopillars that exhibit broadband and enhanced chiroptical response in transmission operation. We use an emerging bottom-up fabrication approach, named glancing angle deposition, to assemble these dielectric metamaterials on a wafer scale. The reported strong chirality and optical anisotropic properties are controllable in terms of both amplitude and operating frequency by simply varying the shape and dimensions of the nanopillars. The presented nanostructures can be used in a plethora of emerging nanophotonic applications, such as chiral sensors, polarization filters, and spin-locked nanowaveguides.

Randomized controlled clinical trial on the efficacy of a novel antimicrobial chewing gum in reducing plaque and gingivitis in adolescent orthodontic patients.

OBJECTIVES: Chewing gums containing antiseptics or other antimicrobial substances may be effective in reducing plaque and gingivitis. Therefore, the aim of this randomized placebo-controlled clinical trial was to investigate the efficacy of a novel antimicrobial chewing gum containing essential oils (cinnamon, lemon, peppermint) and extracts on reduction of dental plaque and gingivitis as well as on oral health-related quality of life (OHRQoL) in adolescent orthodontic patients. MATERIALS: 52 patients (11-22 years of age) were randomly assigned to use a test chewing gum (COVIDGUM, Clevergum) or a commercially available control chewing gum over a period of 10 days. Approximal plaque index (API), papillary bleeding index (PBI) and an OHRQoL questionnaire for children (COHIP-G19) were assessed at baseline (BL), after 10 days (10d) and 30 days (30d). In addition, oral health and oral hygiene related questions of the COHIP-G19 questionnaire were evaluated separately in subscales at each timepoint. Data were analyzed using non-parametrical statistical procedures (α = 0.05). RESULTS: API and PBI decreased significantly over time from BL to 10d and from BL to 30d in both groups, without significant differences between the groups. In both groups, the COHIP-G19 score, oral health subscale and oral hygiene subscale decreased significantly over time. Regarding the oral hygiene subscale, the test group showed significantly better scores at 30d (p = 0.011). CONCLUSION: Both chewing gums performed similarly effective in terms of reducing plaque accumulation and gingival inflammation and improving OHRQoL. CLINICAL RELEVANCE: Chewing gums without antimicrobial ingredients may be sufficient to decrease plaque accumulation and gingival inflammation.

Calcification patterns and morphology of Sella turcica are related to anteroposterior skeletal malocclusions: A cross-sectional study.

BACKGROUND: The sphenoid bone is an irregular, unpaired, symmetrical bone located in the middle of the anterior skull and is involved in craniofacial growth and development. Since the morphology of Sella turcica (ST) is associated with different craniofacial patterns, this study aimed to investigate if there is a correlation between ST morphology on the one hand and sagittal craniofacial patterns on the other hand. METHODS: This study was conducted with a convenience sample that included Brazilian individuals undergoing orthodontic treatment. Lateral cephalograms were used to evaluate the calcification pattern and morphology of ST, as well as skeletal class by analyzing the ANB angle. Pearson's chi-square test with Bonferroni post-hoc test was performed to evaluate the association between ST calcification pattern and morphology, and anteroposterior skeletal malocclusion. The established significance level was 0.05. RESULTS: The study collective was comprised of 305 orthodontic patients (178 (58.4 %) female, 127 (41.6 %) male), who had a mean age of 23.2 (±10.6) years. 131 participants (42.9 %) presented skeletal class I, 142 (46.6%) skeletal Class II, and 32 (10.5%) had a skeletal class III. The degree of prognathism of the mandible showed a homogenous distribution within the study collective (91 (29.9 %) orthognathic, 100 (32.9 %) retrognathic, 113 (37.2 %) prognathic mandible). Concerning the maxilla, 92 (30.2%) individuals presented an orthognathic upper jaw, whereas 60 (19.7%) showed maxillary retrognathism and 153 (50.2%) maxillary prognathism. Compared to patients with skeletal class I, skeletal class III individuals presented significantly more hypertrophic posterior clinoid process (p<0.007) and pyramidal shape of the dorsum of the ST (p<0.038). CONCLUSIONS: Our results suggest that the hypertrophic posterior clinoid process and pyramidal shape of the ST dorsum are more prevalent in individuals with skeletal class III malocclusion.

New insights into the genetics of mandibular retrognathism: novel candidate genes.

PURPOSE: Mandibular retrognathism (MR) is a common skeletal malocclusion in humans with a strong genetic component. Single nucleotide polymorphisms (SNPs) in genes encoding epidermal growth factor (EGF) and EGF receptor (EGFR) could be involved in the etiology of mandibular retrognathism. Therefore, in this study, we investigated whether SNPs in the genes encoding for EGF and EGFR are associated with MR in German teenagers. METHODS: This nested case-control study evaluated German orthodontic patients, aged 10-18 years. DNA, which was isolated from buccal epithelial cells using two cytobrushes, was used for genotyping analysis and digital pretreatment lateral cephalograms were examined to calculate SNB and ANB. Patients with a retrognathic mandible (SNB < 78°) were included as cases, while patients with an orthognathic mandible (SNB = 78-82°) were included as controls. Four SNPs in the genes encoding for EGF and EGFR were chosen and genotyped using real-time PCR. Allele, genotype, and haplotype frequency were compared across groups (α = 5%). RESULTS: Finally, 119 patients were included in this study (45 orthognathic mandible, 74 retrognathic mandible). The minor allele G in rs4444903 (EGF) was statistically more frequent in individuals with an orthognathic mandible (p = 0.008). The haplotype formed by the mutant alleles for rs4444903|rs2237051 (EGF; G|A) was statistically more frequent in the orthognathic mandible group (p = 0.007). The SNPs rs4444903 and rs2237051 in EGF, and rs2227983 in EGFR were statistically associated with a decreasing risk of developing a retrognathic mandible according to univariate and multivariate statistical analysis (p < 0.05). CONCLUSION: SNPs in EGF (rs4444903 and rs2237051) and EGFR (rs2227983) were associated with MR in our German sample and could be genetic biomarkers for early and individualized diagnostic identification of retrognathic mandibular development by means of genetic screening tests.

Ferromagnetic resonators synthesized by metal-organic decomposition epitaxy.

Metal-organic decomposition epitaxy is an economical wet-chemical approach suitable to synthesize high-quality low-spin-damping films for resonator and oscillator applications. This work reports the temperature dependence of ferromagnetic resonances and associated structural and magnetic quantities of yttrium iron garnet nanofilms that coincide with single-crystal values. Despite imperfections originating from wet-chemical deposition and spin coating, the quality factor for out-of-plane and in-plane resonances approaches 600 and 1000, respectively, at room temperature and 40 GHz. These values increase with temperature and are 100 times larger than those offered by commercial devices based on complementary metal-oxide semiconductor voltage-controlled oscillators at comparable production costs.

Mueller matrix imaging microscope using dual continuously rotating anisotropic mirrors.

We demonstrate calibration and operation of a Mueller matrix imaging microscope using dual continuously rotating anisotropic mirrors for polarization state generation and analysis. The mirrors contain highly spatially coherent nanostructure slanted columnar titanium thin films deposited onto optically thick titanium layers on quartz substrates. The first mirror acts as polarization state image generator and the second mirror acts as polarization state image detector. The instrument is calibrated using samples consisting of laterally homogeneous properties such as straight-through-air, a clear aperture linear polarizer, and a clear aperture linear retarder waveplate. Mueller matrix images are determined for spatially varying anisotropic samples consisting of a commercially available (Thorlabs) birefringent resolution target and a spatially patterned titanium slanted columnar thin film deposited onto a glass substrate. Calibration and operation are demonstrated at a single wavelength (530 nm) only, while, in principle, the instrument can operate regardless of wavelength. We refer to this imaging ellipsometry configuration as rotating-anisotropic-mirror-sample-rotating-anisotropic-mirror ellipsometry (RAM-S-RAM-E).

Mueller matrix ellipsometer using dual continuously rotating anisotropic mirrors.

We demonstrate calibration and operation of a single wavelength (660 nm) Mueller matrix ellipsometer in normal transmission configuration using dual continuously rotating anisotropic mirrors. The mirrors contain highly spatially coherent nanostructure slanted columnar titanium thin films deposited onto optically thick gold layers on glass substrates. Upon rotation around the mirror normal axis, sufficient modulation of the Stokes parameters of light reflected at oblique angle of incidence is achieved. Thereby, the mirrors can be used as a polarization state generator and polarization state analyzer in a generalized ellipsometry instrument. A Fourier expansion approach is found sufficient to render and calibrate the effects of the mirror rotations onto the polarized light train within the ellipsometer. The Mueller matrix elements of a set of anisotropic samples consisting of a linear polarizer and a linear retarder are measured and compared with model data, and very good agreement is observed.

Precursor-surface interactions revealed during plasma-enhanced atomic layer deposition of metal oxide thin films by in-situ spectroscopic ellipsometry.

We find that a five-phase (substrate, mixed native oxide and roughness interface layer, metal oxide thin film layer, surface ligand layer, ambient) model with two-dynamic (metal oxide thin film layer thickness and surface ligand layer void fraction) parameters (dynamic dual box model) is sufficient to explain in-situ spectroscopic ellipsometry data measured within and across multiple cycles during plasma-enhanced atomic layer deposition of metal oxide thin films. We demonstrate our dynamic dual box model for analysis of in-situ spectroscopic ellipsometry data in the photon energy range of 0.7-3.4 eV measured with time resolution of few seconds over large numbers of cycles during the growth of titanium oxide (TiO2) and tungsten oxide (WO3) thin films, as examples. We observe cyclic surface roughening with fast kinetics and subsequent roughness reduction with slow kinetics, upon cyclic exposure to precursor materials, leading to oscillations of the metal thin film thickness with small but positive growth per cycle. We explain the cyclic surface roughening by precursor-surface interactions leading to defect creation, and subsequent surface restructuring. Atomic force microscopic images before and after growth, x-ray photoelectron spectroscopy, and x-ray diffraction investigations confirm structural and chemical properties of our thin films. Our proposed dynamic dual box model may be generally applicable to monitor and control metal oxide growth in atomic layer deposition, and we include data for SiO2 and Al2O3 as further examples.

Free Polyethylenimine Enhances Substrate-Mediated Gene Delivery on Titanium Substrates Modified With RGD-Functionalized Poly(acrylic acid) Brushes.

Substrate mediated gene delivery (SMD) is a method of immobilizing DNA complexes to a substrate via covalent attachment or nonspecific adsorption, which allows for increased transgene expression with less DNA compared to traditional bolus delivery. It may also increase cells receptivity to transfection via cell-material interactions. Substrate modifications with poly(acrylic) acid (PAA) brushes may improve SMD by enhancing substrate interactions with DNA complexes via tailored surface chemistry and increasing cellular adhesion via moieties covalently bound to the brushes. Previously, we described a simple method to graft PAA brushes to Ti and further demonstrated conjugation of cell adhesion peptides (i.e., RGD) to the PAA brushes to improve biocompatibility. The objective of this work was to investigate the ability of Ti substrates modified with PAA-RGD brushes (PAA-RGD) to immobilize complexes composed of branched polyethyleneimine and DNA plasmids (bPEI-DNA) and support SMD in NIH/3T3 fibroblasts. Transfection in NIH/3T3 cells cultured on bPEI-DNA complexes immobilized onto PAA-RGD substrates was measured and compared to transfection in cells cultured on control surfaces with immobilized complexes including Flat Ti, PAA brushes modified with a control peptide (RGE), and unmodified PAA. Transfection was two-fold higher in cells cultured on PAA-RGD compared to those cultured on all control substrates. While DNA immobilization measured with radiolabeled DNA indicated that all substrates (PAA-RGD, unmodified PAA, Flat Ti) contained nearly equivalent amounts of loaded DNA, ellipsometric measurements showed that more total mass (i.e., DNA and bPEI, both complexed and free) was immobilized to PAA and PAA-RGD compared to Flat Ti. The increase in adsorbed mass may be attributed to free bPEI, which has been shown to improve transfection. Further transfection investigations showed that removing free bPEI from the immobilized complexes decreased SMD transfection and negated any differences in transfection success between cells cultured on PAA-RGD and on control substrates, suggesting that free bPEI may be beneficial for SMD in cells cultured on bPEI-DNA complexes immobilized on PAA-RGD grafted to Ti. This work demonstrates that substrate modification with PAA-RGD is a feasible method to enhance SMD outcomes on Ti and may be used for future applications such as tissue engineering, gene therapy, and diagnostics.

Tunable plasmonic resonances in Si-Au slanted columnar heterostructure thin films.

We report on fabrication of spatially-coherent columnar plasmonic nanostructure superlattice-type thin films with high porosity and strong optical anisotropy using glancing angle deposition. Subsequent and repeated depositions of silicon and gold lead to nanometer-dimension subcolumns with controlled lengths. We perform generalized spectroscopic ellipsometry measurements and finite element method computations to elucidate the strongly anisotropic optical properties of the highly-porous Si-Au slanted columnar heterostructures. The occurrence of a strongly localized plasmonic mode with displacement pattern reminiscent of a dark quadrupole mode is observed in the vicinity of the gold subcolumns. We demonstrate tuning of this quadrupole-like mode frequency within the near-infrared spectral range by varying the geometry of Si-Au slanted columnar heterostructures. In addition, coupled-plasmon-like and inter-band transition-like modes occur in the visible and ultra-violet spectral regions, respectively. We elucidate an example for the potential use of Si-Au slanted columnar heterostructures as a highly porous plasmonic sensor with optical read out sensitivity to few parts-per-million solvent levels in water.

Biofunctionalization of Titanium Substrates Using Nanoscale Polymer Brushes with Cell Adhesion Peptides.

The grafting of polymer brushes to substrates is a promising method to modify surface properties such as wettability and the affinity toward proteins and cells for applications in microelectronics, biomedical devices, and sensors. Poly(acrylic) acid (PAA) brushes are of high interest because of their stimuli-responsive behavior and the presence of carboxy (COOH) groups, which allow for immobilization of bioactive molecules. The "grafting-to" approach results in homogeneous and well-defined polymer brushes, but, although grafting-to has been demonstrated with PAA brushes on silicon (Si) substrates, it has not been performed on biocompatible materials such as titanium (Ti). Here, we have described a facile method to modify biocompatible Ti substrates with PAA brushes to amplify their substrate functionality. The grafting-to PAA "pseudo" brushes were successfully grafted to Ti substrates and retained their pH-dependent swelling behavior. An RGD peptide was covalently bound to COOH groups of the PAA brushes (PAA-RGD) as a model bioactive group. While NIH/3T3 cell adhesion was significantly decreased on PAA-functionalized Ti substrates, PAA-RGD on Ti had cell adhesion comparable to that of flat Ti at 24 and 48 h, with significantly more cells adhered to PAA-RGD compared to PAA on Ti at 48 h.

Combined quartz crystal microbalance with dissipation (QCM-D) and generalized ellipsometry (GE) to characterize the deposition of titanium dioxide nanoparticles on model rough surfaces.

Measuring the interactions between engineered nanoparticles and natural substrates (e.g. soils and sediments) has been very challenging due to highly heterogeneous and rough natural surfaces. In this study, three-dimensional nanostructured slanted columnar thin films (SCTFs), with well-defined roughness height and spacing, have been used to mimic surface roughness. Interactions between titanium dioxide nanoparticles (TiO2NP), the most extensively manufactured engineered nanomaterials, and SCTF coated surfaces were measured using a quartz crystal microbalance with dissipation monitoring (QCM-D). In parallel, in-situ generalized ellipsometry (GE) was coupled with QCM-D to simultaneously measure the amount of TiO2NP deposited on the surface of SCTF. While GE is insensitive to effects of mechanical water entrapment variations in roughness spaces, we found that the viscoelastic model, a typical QCM-D model analysis approach, overestimates the mass of deposited TiO2NP. This overestimation arises from overlaid frequency changes caused by particle deposition as well as additional water entrapment and partial water displacement upon nanoparticle adsorption. Here, we demonstrate a new approach to model QCM-D data, accounting for both viscoelastic effects and the effects of roughness-retained water. Finally, the porosity of attached TiO2NP layer was determined by coupling the areal mass density determined by QCM-D and independent GE measurements.

The retention of liquid by columnar nanostructured surfaces during quartz crystal microbalance measurements and the effects of adsorption thereon.

HYPOTHESIS: A surface comprising spatially coherent columnar nanostructures is expected to retain intercolumnar liquid during a quartz crystal microbalance measurement due to the surface structure. Part of the liquid retained by the nanostructures may then be displaced by adsorbate. EXPERIMENTS: Slanted columnar nanostructure thin films were designed to vary in height but remain structurally similar, fabricated by glancing angle deposition, and characterized by generalized ellipsometry. A frequency overtone analysis, introduced here, was applied to analyze quartz crystal microbalance data for the exchange of isotope liquids over the nanostructured surfaces and determine the areal inertial mass of structure-retained liquid. The adsorption of cetyltrimethylammonium bromide onto nanostructures was investigated by simultaneous quartz crystal microbalance and generalized ellipsometry measurements. FINDINGS: The areal inertial mass of structure-retained liquid varies linearly with nanostructure height. The proportionality constant is a function of the surface topography and agrees with the generalized ellipsometry-determined nanostructure film porosity, implying that nearly all intercolumnar liquid is retained. We report that for adsorption processes within porous nanostructured films, the quartz crystal microbalance is sensitive not to the combined areal inertial mass of adsorbate and retained liquid but rather to the density difference between adsorbate and liquid due to the volume exchange within the nanostructure film.

Use of precisely sculptured thin film (STF) substrates with generalized ellipsometry to determine spatial distribution of adsorbed fibronectin to nanostructured columnar topographies and effect on cell adhesion.

Sculptured thin film (STF) substrates consist of nanocolumns with precise orientation, intercolumnar spacing, and optical anisotropy, which can be used as model biomaterial substrates to study the effect of homogenous nanotopogrophies on the three-dimensional distribution of adsorbed proteins. Generalized ellipsometry was used to discriminate between the distributions of adsorbed FN either on top of or within the intercolumnar void spaces of STFs, afforded by the optical properties of these precisely crafted substrates. Generalized ellipsometry indicated that STFs with vertical nanocolumns enhanced total FN adsorption two-fold relative to flat control substrates and the FN adsorption studies demonstrate different STF characteristics influence the degree of FN immobilization both on top and within intercolumnar spaces, with increasing spacing and surface area enhancing total protein adsorption. Mouse fibroblasts or mouse mesenchymal stem cells were subsequently cultured on STFs, to investigate the effect of highly ordered and defined nanotopographies on cell adhesion, spreading, and proliferation. All STF nanotopographies investigated in the absence of adsorbed FN were found to significantly enhance cell adhesion relative to flat substrates; and the addition of FN to STFs was found to have cell-dependent effects on enhancing cell-material interactions. Furthermore, the amount of FN adsorbed to the STFs did not correlate with comparative enhancements of cell-material interactions, suggesting that nanotopography predominantly contributes to the biocompatibility of homogenous nanocolumnar surfaces. This is the first study to correlate precisely defined nanostructured features with protein distribution and cell-nanomaterial interactions. STFs demonstrate immense potential as biomaterial surfaces for applications in tissue engineering, drug delivery, and biosensing.

Multilayer graphitic coatings for thermal stabilization of metallic nanostructures.

We demonstrate that graphitic coatings, which consist of multilayer disordered graphene sheets, can be used for the thermal protection of delicate metal nanostructures. We studied cobalt slanted nanopillars grown by glancing angle deposition that were shown to melt at temperatures much lower than the melting point of bulk cobalt. After graphitic coatings were conformally grown over the surfaces of Co nanopillars by chemical vapor deposition, the resulting carbon-coated Co nanostructures retained their morphology at elevated temperatures, which would damage the uncoated structures. Thermal stabilization is also demonstrated for carbon-coated Ti nanopillars. The results of this study may be extended to other metallic and possibly even nonmetallic nanostructures that need to preserve their morphology at elevated temperatures in a broad range of applications.

Visualization of the magnetic structure of sculpted three-dimensional cobalt nanospirals.

In this work, we report on the direct visualization of magnetic structure in sculpted three-dimensional cobalt (Co) nanospirals with a wire diameter of 20 nm and outer spiral diameter of 115 nm and on the magnetic interactions between the nanospirals, using aberration-corrected Lorentz transmission electron microscopy. By analyzing the magnetic domains in three dimensions at the nanoscale, we show that magnetic domain formation in the Co nanospirals is a result of the shape anisotropy dominating over the magnetocrystalline anisotropy of the system. We also show that the strong dipolar magnetic interactions between adjacent closely packed nanospirals leads to their magnetization directions adopting alternating directions to minimize the total magnetostatic energy of the system. Deviations from such magnetization structure can only be explained by analyzing the complex three-dimensional structure of the nanospirals. These nanostructures possess an inherent chirality due to their growth conditions and are of significant importance as nanoscale building blocks in magneto-optical devices.

Generalized ellipsometry in-situ quantification of organic adsorbate attachment within slanted columnar thin films.

We apply generalized ellipsometry, well-known to be sensitive to the optical properties of anisotropic materials, to determine the amount of fibronectin protein that adsorbs onto a Ti slanted columnar thin film from solution. We find that the anisotropic optical properties of the thin film change upon organic adsorption. An optical model for ellipsometry data analysis incorporates an anisotropic Bruggeman effective medium approximation. We find that differences in experimental data from before and after fibronectin adsorption can be solely attributable to the uptake of fibronectin within the slanted columnar thin film. Simultaneous, in-situ generalized ellipsometry and quartz crystal microbalance measurements show excellent agreement on the amount and rate of fibronectin adsorption. Quantitative characterization of organic materials within three-dimensional, optically anisotropic slanted columnar thin films could permit their use in optical sensor applications.

Stereotactic fractionated radiotherapy for Klatskin tumours.

BACKGROUND AND PURPOSE: In spite of various efforts perihilar cholangiocellular carcinoma (Klatskin tumour) has still a bad prognosis. The treatment of patients with inoperable Klatskin tumours by stereotactic fractionated radiotherapy (SFRT) was analysed retrospectively. PATIENTS, METHODS AND MATERIALS: In our department 13 patients were treated for Klatskin tumours by SFRT (32-56 Gy, 3 x 4 Gy/week) from 1998 to 2008. The treatment technique was developed from stereotactic body frame radiotherapy to image guided (IGRT) stereotactic radiotherapy with control of patient positioning by cone beam computer tomography (CBCT). 6/13 patients received additional chemotherapy before or after SFRT. RESULTS: A median survival of 33.5 (6.6-60.4) months after diagnosis was reached by SFRT. The median time of freedom from tumour progression was 32.5 (6.1-60.4, last patient died without tumour progression) months. The therapy was tolerated very well. Nausea was the most common side effect. 5/13 patients suffered from recurrent cholangitis caused and enhanced by the primary tumour and drainages or stents in the bile ducts. CONCLUSIONS: In the context of reaching local control being still the main problem of Klatskin tumour patients, SFRT seems to be a very promising method for the treatment of these tumours.

Association between chronotype and the constructs of the Three-Factor-Eating-Questionnaire.

The aim of this study was to explore associations between chronotype and the Three-Factor-Eating-Questionnaire. We found a positive association between morningness and dietary restraint and negative correlations between morningness and disinhibition and perceived hunger. Further, there was an association between morningness and flexible control. BMI tended to be negatively associated with morningness and correlated with disinhibition and with the sub-scale RC7. No association was found between BMI and cognitive restraint, hunger and flexible control. Also, no relationships existed between sleep length on weekdays or on weekends and BMI or eating.