Effects of nanomodified titanium surfaces considering bacterial colonization and viability of osteoblasts and fibroblasts.

This study investigates nanostructured titanium surfaces (Ti2 spikes) that promote the viability of osteoblasts and fibroblasts and prevent bacterial colonisation. Helium ion irradiation was adopted to produce nanometric-sized cones on titanium. Human osteoblasts (hFOB) and human gingiva fibroblasts (hGF) were used for analysis. A viability and a cytotoxicity assay were conducted to evaluate the lactate dehydrogenase (LDH) activity and assess cell damage in Ti2 spikes compared to titanium discs with a sandblasted and acid-etched (Ti2 SLA) surface. The antibacterial activity was investigated against Escherichia coli, Streptococcus mutans, Fusobacterium nucleatum, and Porphyromonas gingivalis. In the course of the cultivation, both hGF and hFOB demonstrated significantly reduced viability on the Ti2 spikes surface. hGF cells exhibited a slight but significant increase in LDH release. In contrast, hFOB showed reduced cytotoxicity on this surface. On the Ti2 spikes surface, hGF cells exhibited a significant reduction in gene expression of VCL, Src-1, and ITGα5. However, the integrin subunits ITGα1 and ITGα3 showed upregulation on the Ti2 spikes surface. The Ti2 spikes surface significantly increased the expression of almost all osteogenic markers. The results of conventional culturing demonstrated a statistically significant decrease in the number of viable cells for S. mutans, F. nucleaum, and greater quantities of P. gingivalis on Ti2 spikes surface compared to control. However, no such reduction was detected for E. coli. The long-term success of implants relies on establishing and maintaining hard and soft peri-implant tissues. Ti2 spikes represent a novel and promising approach to enhance osseointegration and optimize biocompatibility.

Novel Titanium Nanospike Structure Using Low-Energy Helium Ion Bombardment for the Transgingival Part of a Dental Implant.

AIM(S): The aim of the study was to fabricate a nanospike surface on a titanium alloy surface using a newly established method of low-energy helium ion bombardment. Various methods to achieve nanospike formation on titanium have been introduced recently, and their antibacterial properties have been mainly investigated with respect to Escherichia coli and Staphylococcus aureus. Oral pathogens such as Porphyromonas gingivalis play an important role in the development of peri-implantitis. For that reason, the antibacterial properties of the novel, nanostructured titanium surface against P. gingivalis were assessed, and a possible effect on the viability of gingival fibroblasts was evaluated. MATERIALS AND METHODS: Helium sputtering was employed for developing titanium surfaces with nanospikes of 500 nm (ND) in height; commercially available smooth-machined (MD) and sandblasted and acid-etched titanium disks (SLA) were used as controls. Surface structure characterization was performed through scanning electron microscopy (SEM) and atomic force microscopy (AFM). Following incubation with P. gingivalis, antibacterial properties were determined via conventional culturing and SEM. Additionally, the viability of human gingival fibroblasts (HGFs) was tested through MTT assay, and cell morphology was assessed through SEM. RESULTS: SEM images confirmed the successful establishment of a nanospike surface with required heights, albeit with heterogeneity. AFM images of the 500 nm nanospike surface revealed that the roughness is dominated by large-scale hills and valleys. For frame sizes of 5 × 5 µm and smaller, the average roughness is dominated by the height of the titanium spikes. ND successfully induces dysmorphisms within P. gingivalis cultures following the incubation period, while conventional culturing reveals a 17% and 20% reduction for ND compared to MD and SLA, respectively. Moreover, the nanospike surfaces did not affect the viability of human growth fibroblasts despite their sharp surface. CONCLUSION(S): This study successfully developed a novel titanium-nanospike-based structuration technique for titanium surfaces. In addition, the nanospikes did not hinder gingival fibroblast viability. Enhanced antimicrobial effects for such a novel nanospike-based resurfacing technique can be achieved through further optimizations for nanospike spacing and height parameters.

Plasma-assisted catalytic formation of ammonia in N2-H2 plasma on a tungsten surface.

Plasma catalysis has drawn attention in the past few decades as a possible alternative to the Haber-Bosch process for ammonia production. In particular, radio frequency plasma assisted catalysis has the advantage of its adaptability to the industrial scale. However, in the past years, very few experimental studies have focused on the synthesis of ammonia from nitrogen/hydrogen radio frequency plasma. As a consequence, to date, there has been little agreement about the complex mechanisms underlying the radio frequency plasma-catalyst interactions. Gaining such an understanding is therefore essential for exploiting the potential of radio frequency plasma catalysis for ammonia production. In this study, we present results of ammonia formation from a nitrogen/hydrogen radio frequency plasma both without and with a tungsten catalyst for different initial nitrogen ratios. High yields of ammonia up to 32% at 25/75% of nitrogen/hydrogen were obtained using a combination of radio frequency low pressure plasma and a W surface as a catalyst. Furthermore, based on chemical analysis of the catalytic surface composition, a formation pathway of ammonia via the Eley-Rideal mechanism between adsorbed nitrogen and hydrogen from the gas phase is presented.

Valence band behaviour of zirconium oxide, Photoelectron and Auger spectroscopy study.

In this study X-ray Photoelectron Spectroscopy and Ultraviolet Photoelectron Spectroscopy were combined to investigate the effect of oxygen incorporation on the valence band behaviour of ZrOx. The Auger transitions involving valence bands are found to mimic the self-folded density of state measured using Ultraviolet Photoelectron Spectroscopy. The valence band once constructed in a sub-oxide form, stays at a fixed energy position despite the change in the stoichiometry. This behaviour is found to be useful in setting a reference for X-ray Photoelectron Spectroscopy charge correction. The results of the charged corrected spectra were compared to other methods and found to be in great agreement. Finally, a correlation between the core-level binding energy and the structural property of ZrOx is given.

Transoid-to-Cisoid Conformation Changes of Single Molecules on Surfaces Triggered by Metal Coordination.

Conformational isomers are stereoisomers that can interconvert over low potential barriers by rotation around a single bond. However, such bond rotation is hampered by geometrical constraints when molecules are adsorbed on surfaces. Here, we show that the adsorption of 4,4'-bis(4-carboxyphenyl)-6,6'-dimethyl-2,2'-bipyridine molecules on surfaces leads to the appearance of prochiral single molecules on NiO(001) and to enantiopure supramolecular domains on Au(111) surfaces containing the transoid-molecule conformation. Upon additional Fe adatom deposition, molecules undergo a controlled interconversion from a transoid-to-cisoid conformation as a result of coordination of the Fe atoms to the 2,2'-bipyridine moieties. As confirmed by atomic force microscopy images and X-ray photoelectron spectroscopy measurements, the resulting molecular structures become irreversibly achiral.

Sex differences in light sensitivity impact on brightness perception, vigilant attention and sleep in humans.

Artificial light endows a "round-the-clock", 24-h/7-d society. Chronic exposure to light at night contributes to health hazards for humans, including disorders of sleep. Yet the influence of inter-individual traits, such as sex-differences, on light sensitivity remains to be established. Here we investigated potential sex-differences to evening light exposure of 40 lx at 6500 K (blue-enriched) or at 2500 K (non-blue-enriched), and their impact on brightness perception, vigilant attention and sleep physiology. In contrast to women, men had higher brightness perception and faster reaction times in a sustained attention task during blue-enriched light than non-blue-enriched. After blue-enriched light exposure, men had significantly higher all-night frontal NREM sleep slow-wave activity (SWA: 2-4 Hz), than women, particularly during the beginning of the sleep episode. Furthermore, brightness perception during blue-enriched light significantly predicted men's improved sustained attention performance and increased frontal NREM SWA. Our data indicate that, in contrast to women, men show a stronger response to blue-enriched light in the late evening even at very low light levels (40lux), as indexed by increased vigilant attention and sleep EEG hallmarks. Collectively, the data indicate that sex differences in light sensitivity might play a key role for ensuring the success of individually-targeted light interventions.

Nanostructuring of an alkali halide surface by low temperature plasma exposure.

Templating insulating surfaces at the nanoscale is an interesting prospect for applications that involve the adsorption of molecules or nanoparticles where electronic decoupling of the adsorbed species from the substrate is needed. In this study, we present a method to structure alkali halide surfaces at the nanoscale using a combination of low temperature plasma exposure and annealing, and characterize the surfaces by atomic force microscopy. We find that nanostructurating can be controlled by the duration of the exposure, the atomic mass of the plasma gas and the subsequent step-by-step annealing process. In contrast to previous studies with electron or high energy (few keV) ion irradiation, our approach of employing moderate particle energy (10-15 eV Ar+ or He+ ions) results in fine nanostructuring at length scales of nanometers and even single atom vacancies.

Surface chemistry of rare-earth oxide surfaces at ambient conditions: reactions with water and hydrocarbons.

Rare-earth (RE) oxide surfaces are of significant importance for catalysis and were recently reported to possess intrinsic hydrophobicity. The surface chemistry of these oxides in the low temperature regime, however, remains to a large extent unexplored. The reactions occurring at RE surfaces at room temperature (RT) in real air environment, in particular, in presence of polycyclic aromatic hydrocarbons (PAHs), were not addressed until now. Discovering these reactions would shed light onto intermediate steps occurring in automotive exhaust catalysts before reaching the final high operational temperature and full conversion of organics. Here we first address physical properties of the RE oxide, nitride and fluoride surfaces modified by exposure to ambient air and then we report a room temperature reaction between PAH and RE oxide surfaces, exemplified by tetracene (C18H12) on a Gd2O3. Our study evidences a novel effect - oxidation of higher hydrocarbons at significantly lower temperatures (~300 K) than previously reported (>500 K). The evolution of the surface chemical composition of RE compounds in ambient air is investigated and correlated with the surface wetting. Our surprising results reveal the complex behavior of RE surfaces and motivate follow-up studies of reactions between PAH and catalytic surfaces at the single molecule level.

Blue blocker glasses as a countermeasure for alerting effects of evening light-emitting diode screen exposure in male teenagers.

PURPOSE: Adolescents prefer sleep and wake times that are considerably delayed compared with younger children or adults. Concomitantly, multimedia use in the evening is prevalent among teenagers and involves light exposure, particularly in the blue-wavelength range to which the biological clock and its associated arousal promotion system is the most sensitive. We investigated whether the use of blue light-blocking glasses (BB) during the evening, while sitting in front of a light-emitting diode (LED) computer screen, favors sleep initiating mechanisms at the subjective, cognitive, and physiological level. METHODS: The ambulatory part of the study comprised 2 weeks during which the sleep-wake cycle, evening light exposure, and multimedia screen use were monitored in thirteen 15- to 17-year-old healthy male volunteers. BB or clear lenses as control glasses were worn in a counterbalanced crossover design for 1 week each, during the evening hours while using LED screens. Afterward, participants entered the laboratory and underwent an evening blue light-enriched LED screen exposure during which they wore the same glasses as during the preceding week. Salivary melatonin, subjective sleepiness, and vigilant attention were regularly assayed, and subsequent sleep was recorded by polysomnography. RESULTS: Compared with clear lenses, BB significantly attenuated LED-induced melatonin suppression in the evening and decreased vigilant attention and subjective alertness before bedtime. Visually scored sleep stages and behavioral measures collected the morning after were not modified. CONCLUSIONS: BB glasses may be useful in adolescents as a countermeasure for alerting effects induced by light exposure through LED screens and therefore potentially impede the negative effects modern lighting imposes on circadian physiology in the evening.

Morphological changes of tungsten surfaces by low-flux helium plasma treatment and helium incorporation via magnetron sputtering.

The effect of helium on the tungsten microstructure was investigated first by exposure to a radio frequency driven helium plasma with fluxes of the order of 1 × 10(19) m(-2) s(-1) and second by helium incorporation via magnetron sputtering. Roughening of the surface and the creation of pinholes were observed when exposing poly- and nanocrystalline tungsten samples to low-flux plasma. A coating process using an excess of helium besides argon in the process gas mixture leads to a porous thin film and a granular surface structure whereas gas mixture ratios of up to 50% He/Ar (in terms of their partial pressures) lead to a dense structure. The presence of helium in the deposited film was confirmed with glow-discharge optical emission spectroscopy and thermal desorption measurements. Latter revealed that the highest fraction of the embedded helium atoms desorb at approximately 1500 K. Identical plasma treatments at various temperatures showed strongest modifications of the surface at 1500 K, which is attributed to the massive activation of helium singly bond to a single vacancy inside the film. Thus, an efficient way of preparing nanostructured tungsten surfaces and porous tungsten films at low fluxes was found.

Acute exposure to evening blue-enriched light impacts on human sleep.

Light in the short wavelength range (blue light: 446-483 nm) elicits direct effects on human melatonin secretion, alertness and cognitive performance via non-image-forming photoreceptors. However, the impact of blue-enriched polychromatic light on human sleep architecture and sleep electroencephalographic activity remains fairly unknown. In this study we investigated sleep structure and sleep electroencephalographic characteristics of 30 healthy young participants (16 men, 14 women; age range 20-31 years) following 2 h of evening light exposure to polychromatic light at 6500 K, 2500 K and 3000 K. Sleep structure across the first three non-rapid eye movement non-rapid eye movement - rapid eye movement sleep cycles did not differ significantly with respect to the light conditions. All-night non-rapid eye movement sleep electroencephalographic power density indicated that exposure to light at 6500 K resulted in a tendency for less frontal non-rapid eye movement electroencephalographic power density, compared to light at 2500 K and 3000 K. The dynamics of non-rapid eye movement electroencephalographic slow wave activity (2.0-4.0 Hz), a functional index of homeostatic sleep pressure, were such that slow wave activity was reduced significantly during the first sleep cycle after light at 6500 K compared to light at 2500 K and 3000 K, particularly in the frontal derivation. Our data suggest that exposure to blue-enriched polychromatic light at relatively low room light levels impacts upon homeostatic sleep regulation, as indexed by reduction in frontal slow wave activity during the first non-rapid eye movement episode.

Pure hydrogen low-temperature plasma exposure of HOPG and graphene: Graphane formation?

Single- and multilayer graphene and highly ordered pyrolytic graphite (HOPG) were exposed to a pure hydrogen low-temperature plasma (LTP). Characterizations include various experimental techniques such as photoelectron spectroscopy, Raman spectroscopy and scanning probe microscopy. Our photoemission measurement shows that hydrogen LTP exposed HOPG has a diamond-like valence-band structure, which suggests double-sided hydrogenation. With the scanning tunneling microscopy technique, various atomic-scale charge-density patterns were observed, which may be associated with different C-H conformers. Hydrogen-LTP-exposed graphene on SiO(2) has a Raman spectrum in which the D peak to G peak ratio is over 4, associated with hydrogenation on both sides. A very low defect density was observed in the scanning probe microscopy measurements, which enables a reverse transformation to graphene. Hydrogen-LTP-exposed HOPG possesses a high thermal stability, and therefore, this transformation requires annealing at over 1000 °C.

Palladium-catalyzed cyanomethylation of aryl halides through domino Suzuki coupling-isoxazole fragmentation.

A one-pot protocol for the cyanomethylation of aryl halides through a palladium-catalyzed reaction with isoxazole-4-boronic acid pinacol ester was developed. Mechanistically, the reaction proceeds through (1) Suzuki coupling, (2) base-induced fragmentation, and (3) deformylation as shown by characterization of all postulated intermediates. Under optimized conditions (PdCl(2)dppf, KF, DMSO/H(2)O, 130 °C) a broad spectrum of aryl bromides could be converted into arylacetonitriles with up to 88% yield.

Non-visual effects of light on melatonin, alertness and cognitive performance: can blue-enriched light keep us alert?

BACKGROUND: Light exposure can cascade numerous effects on the human circadian process via the non-imaging forming system, whose spectral relevance is highest in the short-wavelength range. Here we investigated if commercially available compact fluorescent lamps with different colour temperatures can impact on alertness and cognitive performance. METHODS: Sixteen healthy young men were studied in a balanced cross-over design with light exposure of 3 different light settings (compact fluorescent lamps with light of 40 lux at 6500K and at 2500K and incandescent lamps of 40 lux at 3000K) during 2 h in the evening. RESULTS: Exposure to light at 6500K induced greater melatonin suppression, together with enhanced subjective alertness, well-being and visual comfort. With respect to cognitive performance, light at 6500K led to significantly faster reaction times in tasks associated with sustained attention (Psychomotor Vigilance and GO/NOGO Task), but not in tasks associated with executive function (Paced Visual Serial Addition Task). This cognitive improvement was strongly related with attenuated salivary melatonin levels, particularly for the light condition at 6500K. CONCLUSIONS: Our findings suggest that the sensitivity of the human alerting and cognitive response to polychromatic light at levels as low as 40 lux, is blue-shifted relative to the three-cone visual photopic system. Thus, the selection of commercially available compact fluorescent lights with different colour temperatures significantly impacts on circadian physiology and cognitive performance at home and in the workplace.

Wavelength-dependent effects of evening light exposure on sleep architecture and sleep EEG power density in men.

Light strongly influences the circadian timing system in humans via non-image-forming photoreceptors in the retinal ganglion cells. Their spectral sensitivity is highest in the short-wavelength range of the visible light spectrum as demonstrated by melatonin suppression, circadian phase shifting, acute physiological responses, and subjective alertness. We tested the impact of short wavelength light (460 nm) on sleep EEG power spectra and sleep architecture. We hypothesized that its acute action on sleep is similar in magnitude to reported effects for polychromatic light at higher intensities and stronger than longer wavelength light (550 nm). The sleep EEGs of eight young men were analyzed after 2-h evening exposure to blue (460 nm) and green (550 nm) light of equal photon densities (2.8 x 10(13) photons x cm(-2) x s(-1)) and to dark (0 lux) under constant posture conditions. The time course of EEG slow-wave activity (SWA; 0.75-4.5 Hz) across sleep cycles after blue light at 460 nm was changed such that SWA was slightly reduced in the first and significantly increased during the third sleep cycle in parietal and occipital brain regions. Moreover, blue light significantly shortened rapid eye movement (REM) sleep duration during these two sleep cycles. Thus the light effects on the dynamics of SWA and REM sleep durations were blue shifted relative to the three-cone visual photopic system probably mediated by the circadian, non-image-forming visual system. Our results can be interpreted in terms of an induction of a circadian phase delay and/or repercussions of a stronger alerting effect after blue light, persisting into the sleep episode.

High sensitivity of human melatonin, alertness, thermoregulation, and heart rate to short wavelength light.

Light can elicit acute physiological and alerting responses in humans, the magnitude of which depends on the timing, intensity, and duration of light exposure. Here, we report that the alerting response of light as well as its effects on thermoregulation and heart rate are also wavelength dependent. Exposure to 2 h of monochromatic light at 460 nm in the late evening induced a significantly greater melatonin suppression than occurred with 550-nm monochromatic light, concomitant with a significantly greater alerting response and increased core body temperature and heart rate ( approximately 2.8 x 10(13) photons/cm(2)/sec for each light treatment). Light diminished the distal-proximal skin temperature gradient, a measure of the degree of vasoconstriction, independent of wavelength. Nonclassical ocular photoreceptors with peak sensitivity around 460 nm have been found to regulate circadian rhythm function as measured by melatonin suppression and phase shifting. Our findings-that the sensitivity of the human alerting response to light and its thermoregulatory sequelae are blue-shifted relative to the three-cone visual photopic system-indicate an additional role for these novel photoreceptors in modifying human alertness, thermophysiology, and heart rate.