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For centuries, artisans have harnessed gold nanoparticles to imbue their creations with the vibrant hues that captivate the eye through interactions with visible light. In modern times, these distinct optoelectronic characteristics have pivoted toward the forefront of innovative technologies, finding their niche in advanced applications from solar energy to medicine, overshadowing their artistic heritage. This investigation reimagines the utilitarian scope of gold by innovating the optical characteristics of gold-titania nanostructures. This allows for an expanded palette of colors that retain the value of the precious metal. We employ nanostructured TiO2 in a high-pressure-high-temperature sintering technique that stabilizes Au nanoparticles, thwarting coalescence, and Oswald ripening. Further refinement is possible by engineering TiO2 color centers through the introduction of oxygen vacancies and Ti3+ ions, which aid in creating an opulent high-karat black-gold, but preserve the mechanical attributes essential to the integrity and function of the final product.
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Regular physical exercise is known to lower the incidence of age-related eye diseases. We aimed to assess the acute chorioretinal alterations in older adults following intense physical strain. Seventeen senior elite athletes were recruited who underwent an aerobic exercise on a cycle ergometer and macular scanning by optical coherence tomography. A significant thinning of the entire retina was observed 1 min after exercise, followed by a thickening at 5 min, after which the thickness returned to baseline. This trend was similar in almost every single retinal layer, although a significant change was observed only in the inner retina. Choroidal thickness changes were neither significant nor did they correlate with the thickness changes of intraretinal layers. The mechanism of how these immediate retinal changes chronically impact age-related sight-threatening pathologies that, in turn, result in a substantially reduced quality of life warrants further investigation on nontrained older adults as well.
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Qualidade de Vida , Retina , Humanos , Idoso , Retina/diagnóstico por imagem , Retina/patologia , Corioide/diagnóstico por imagem , Corioide/patologia , Exercício Físico , Tomografia de Coerência Óptica/métodosRESUMO
PURPOSE: There is abundant evidence on the benefits of physical activity on cardiovascular health. However, there are only few data on the acute effects of physical exercise on the retina and choroid. Our aim was the in vivo examination of chorioretinal alterations following short intense physical activity by spectral domain optical coherence tomography (SD-OCT). METHODS: Twenty-one eyes of 21 healthy, young subjects (mean age 22.5 ± 4.1 years, 15 males and 6 females) were recruited. Macular scanning with a SD-OCT was performed before and following a vita maxima-type physical strain exercise on a rowing ergometer until complete fatigue. Follow-up OCT scans were performed 1, 5, 15, 30 and 60 minutes following the exercise. The OCT images were exported and analyzed using our custom-built OCTRIMA 3D software and the thickness of 7 retinal layers was calculated, along with semi-automated measurement of the choroidal thickness. One-way ANOVA analysis was performed followed by Dunnett post hoc test for the thickness change compared to baseline and the correlation between performance and thickness change has also been calculated. The level of significance was set at 0.001. RESULTS: We observed a significant thinning of the total retina 1 minute post-exercise (-7.3 ± 0.6 µm, p < 0.001) which was followed by a significant thickening by 5 and 15 minutes (+3.6 ± 0.6 µm and +4.0 ± 0.6 µm, respectively, both p <0.001). Post-exercise retinal thickness returned to baseline by 30 minutes. This trend was present throughout the most layers of the retina, with significant changes in the ganglion cell-inner plexiform layer complex, (-1.3 ± 0.1 µm, +0.6 ± 0.1 µm and +0.7 ± 0.1 µm, respectively, p <0.001 for all), in the inner nuclear layer at 1 and 5 minutes (-0.8 ± 0.1 µm and +0.8 ± 0.1 µm, respectively, p <0.001 for both), in the outer nuclear layer-photoreceptor inner segment complex at 5 minute (+2.3 ± 0.4 µm, p <0.001 for all) and in the interdigitation zone-retinal pigment epithelium complex at 1 and 15 minutes (-3.3 ± 0.4 µm and +1.8 ± 0.4 µm, respectively, p <0.001 for both). There was no significant change in choroidal thickness; however, we could detect a tendency towards thinning at 1, 15, and 30 minutes following exercise. The observed changes in thickness change did not correlate with performance. Similar trends were observed in both professional and amateur sportsmen (n = 15 and n = 6, respectively). The absolute changes in choroidal thickness did not show any correlation with the thickness changes of the intraretinal layers. CONCLUSIONS: Our study implies that in young adults, intense physical exercise has an acute effect on the granular layers of the retina, resulting in thinning followed by rebound thickening before normalization. We could not identify any clear correlation with either choroidal changes or performance that might explain our observations, and hence the exact mechanism warrants further clarification. We believe that a combination of vascular and mechanic changes is behind the observed trends.
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Corioide , Tomografia de Coerência Óptica , Adolescente , Adulto , Corioide/irrigação sanguínea , Corioide/diagnóstico por imagem , Exercício Físico , Feminino , Humanos , Masculino , Retina/diagnóstico por imagem , Epitélio Pigmentado da Retina , Tomografia de Coerência Óptica/métodos , Adulto JovemRESUMO
AIM: Assessment of intelligence and executive function in 9-10-year-old preterm children as compared to a full-term comparison group and to reveal the background of the individual differences in the outcomes by analyzing the effects of perinatal and social-economic factors. METHOD: Seventy-two preterm children (divided into two groups: 32 extremely low birth weight, 40 very low birth weight) and a matched group of 33 healthy full-term children, aged 9-10 years, were tested using the Wechsler Intelligence Scales for Children (WISC-IV) and digital versions of tasks measuring executive function. As background information perinatal variables and maternal education were entered in the analysis. RESULTS: In the WISC-IV all three groups performed in the normal range. The preterm children, particularly the ELBW subgroup, scored significantly lower than the full-term comparison group in several outcome measures. Behind the group means there were massive scatters of the individual scores. Lower maternal education, male gender, and bronchopulmonary dysplasia (BPD) increased the risk for performance deficits. CONCLUSION: Low-to-moderate risk preterm children as groups are disadvantaged in the development of intelligence and executive function as compared to healthy full-term children even until school-age. However, with appropriate protective factors they may have chances to develop comparably with their full-term, non-risk counterparts.
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Função Executiva , Inteligência , Peso ao Nascer , Criança , Humanos , Recém-Nascido de Peso Extremamente Baixo ao Nascer , Recém-Nascido , Masculino , Escalas de WechslerRESUMO
Interest in fast and easy detection of high-energy radiation (x-, γ-rays and neutrons) is closely related to numerous practical applications ranging from biomedicine and industry to homeland security issues. In this regard, crystals of hybrid halide perovskite have proven to be excellent detectors of x- and γ-rays, offering exceptionally high sensitivities in parallel to the ease of design and handling. Here, we demonstrate that by assembling a methylammonium lead tri-bromide perovskite single crystal (CH3NH3PbBr3 SC) with a Gadolinium (Gd) foil, one can very efficiently detect a flux of thermal neutrons. The neutrons absorbed by the Gd foil turn into γ-rays, which photo-generate charge carriers in the CH3NH3PbBr3 SC. The induced photo-carriers contribute to the electric current, which can easily be measured, providing information on the radiation intensity of thermal neutrons. The dependence on the beam size, bias voltage and the converting distance is investigated. To ensure stable and efficient charge extraction, the perovskite SCs were equipped with carbon electrodes. Furthermore, other types of conversion layers were also tested, including borated polyethylene sheets as well as Gd grains and Gd2O3 pellets directly engulfed into the SCs. Monte Carlo N-Particle (MCNP) radiation transport code calculations quantitatively confirmed the detection mechanism herein proposed.
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Organic-inorganic lead halide perovskite (CH3NH3PbI3) solar cells have surpassed 25% power conversion efficiency, being ready for industrial-scale production of cheap photovoltaic (PV) panels. In this action, the major hurdle is its lead content, which in case of device failure, could be washed into the soil, entering the food chain. Since there is a zero tolerance on lead in the human organism, this health hazard is a critical obstacle for commercialization. Here, we propose a solution to this problem by incorporating phosphate salts (e.g., (NH4)2HPO4) in PV and other perovskite-based optoelectronic devices in various architectures. Phosphate salts do not react with CH3NH3PbI3 and do not alter its advantageous optoelectronic properties, but in a wet environment, they react immediately with lead, forming a highly insoluble compound, precluding this way the spread of lead into the environment. It is expected that this study will stimulate research, enabling lead halide perovskite solar cells to reach a similar environmental risk category as the commercially available, nonwater-soluble heavy metal-containing CdTe and gallium diselenide technologies.
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PURPOSE: Macular structure is poorly evaluated in early-treated phenylketonuria (ETPKU). To evaluate potential changes, we aimed to examine retinas of PKU patients using optical coherence tomography (OCT) with additional OCT angiography (OCTA) and compare the results to healthy controls. METHODS: A total of 100 adults were recruited in this monocentric, case-control study: 50 patients with ETPKU (mean age: 30.66 ± 8.00 years) and 50 healthy controls (mean age: 30.45 ± 7.18 years). Macular thickness, vessel density and flow area of the right eye was assessed with spectral domain OCT angiography SD-OCT(A). Macular microstructural data between the ETPKU and control group was compared. In the ETPKU group, the relationship between visual functional parameters (best corrected visual acuity [VA], spherical equivalent [SE], contrast sensitivity [CS] and near stereoacuity) and microstructural alterations was examined. The dependency of OCT(A) values on serum phenylalanine (Phe) level was analysed. RESULTS: There was significant average parafoveal and perifoveal total retinal layer thinning in ETPKU patients compared to healthy controls (p < 0.016 and p < 0.001, respectively), while the foveal region remained unchanged in the ETPKU group. Whole macular and parafoveal superficial capillary plexus density was significantly decreased in ETPKU compared to controls (p < 0.001). There were no significant differences in the foveal avascular zone, nonflow area, macular superficial and deep capillary plexus between the groups. The temporal parafoveal inner retinal layer thickness was found to negatively correlate with individual Phe levels (r = -0.35, p = 0.042). There was no difference in vascular density and retinal thickness in the subgroup analysis of patients with good therapy adherence compared to patients on a relaxed diet. CONCLUSIONS: Durable elevation in Phe levels are only partially associated with macular retinal structural changes. However, therapy adherence might not influence these ophthalmological complications.
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X-ray photon detection is important for a wide range of applications. The highest demand, however, comes from medical imaging, which requires cost-effective, high-resolution detectors operating at low-photon flux, therefore stimulating the search for novel materials and new approaches. Recently, hybrid halide perovskite CH3NH3PbI3 (MAPbI3) has attracted considerable attention due to its advantageous optoelectronic properties and low fabrication costs. The presence of heavy atoms, providing a high scattering cross-section for photons, makes this material a perfect candidate for X-ray detection. Despite the already-successful demonstrations of efficiency in detection, its integration into standard microelectronics fabrication processes is still pending. Here, we demonstrate a promising method for building X-ray detector units by 3D aerosol jet printing with a record sensitivity of 2.2 × 108 µC Gyair-1 cm-2 when detecting 8 keV photons at dose rates below 1 µGy/s (detection limit 0.12 µGy/s), a 4-fold improvement on the best-in-class devices. An introduction of MAPbI3-based detection into medical imaging would significantly reduce health hazards related to the strongly ionizing X-rays' photons.
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Gamma-rays (γ-rays), wherever present, e.g., in medicine, nuclear environment, or homeland security, due to their strong impact on biological matter, should be closely monitored. There is a need for simple, sensitive γ-ray detectors at affordable prices. Here, it is shown that γ-ray detectors based on crystals of methylammonium lead tribromide (MAPbBr3) ideally meet these requirements. Specifically, the γ-rays incident on a MAPbBr3 crystal generates photocarriers with a high mobility-lifetime product, allowing radiation detection by photocurrent measurements at room temperatures. Moreover, the MAPbBr3 crystal-based detectors, equipped with improved carbon electrodes, can operate at low bias (≈1.0 V), hence being suitable for applications in energy-sparse environments, including space. The γ-ray detectors reported herein are exposed to radiation from a 60Co source at dose rates up to 2.3 Gy h-1 under ambient conditions for over 100 h, without any sign of degradation. The excellent radiation tolerance stems from the intrinsic structural plasticity of the organic-inorganic halide perovskites, which can be attributed to a defect-healing process by fast ion migration at the nanoscale level. The sensitivity of the γ-ray detection upon volume is tested for MAPbBr3 crystals reaching up to 1000 cm3 (3.3 kg in weight) grown by a unique crystal growth technique.
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PURPOSE: Retinal changes are poorly described in early treated phenylketonuria (ETPKU). We aimed to investigate possible visual functional and ocular microstructural changes in adult patients with ETPKU. Optical coherence tomography (OCT) and its angiography (OCTA) data from patients with PKU were compared to healthy controls. METHODS: In this prospective, monocentric, cross-sectional, case-control study 50 patients with ETPKU and 50 healthy subjects were evaluated with OCT and OCTA. Measurements were performed on right eyes. The following visual function parameters were studied: best corrected visual acuity (BCVA), spherical equivalent (SE), contrast sensitivity and near stereoacuity; microstructural parameters: retinal nerve fiber layer thickness (RNFLT), ganglion cell layer (GCC) thickness, focal loss of volume (FLV), global loss of volume (GLV), peripapillary, papillary vessel density (VD), ocular axial length (AL) and intraocular pressure (IOP). RESULTS: Among functional tests there were significant differences in contrast sensitivity at 1.5 (p < 0.001), 6 (p < 0.013), 12 (p < 0.001), 18 (p < 0.003) cycles per degree, in near stereoacuity (Titmus Wirt circles, p < 0.001) and in best corrected visual acuity (BCVA, p < 0.001). A statistically significant, moderate positive linear correlation was observed between BCVA and average Phe levels over the last ten years (ß = 0.49, p < 0.001). The average (p < 0.001), superior (p < 0.001) inferior GCC (p < 0.001), the FLV (p < 0.003), GLV (p < 0.001) and the average RNFLT (p < 0.004) values of the PKU group were significantly lower than the controls. The serum phenylalanine level (Phe) in the PKU group negatively correlated with inferior (-0.32, p < 0.007), superior (r = -0.26, p < 0.028) and average (-0.29 p < 0.014) RNFL and with AL (-0.32, p < 0.026). In AL we detected a significant difference (p < 0.04) between the good and suboptimal dietary controlled group. There was no significant difference between the ETPKU and control group in the measured vessel density parameters and in IOP. CONCLUSIONS: Our results suggest that functional and ocular microstructural defects are present in patients with PKU, and some of them may depend on dietary control. The mechanism is unclear, but the correlation indicates the importance of strict dietary control in terms of preservation of retinal functions.
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In the last couple decades, several viral outbreaks resulting in epidemics and pandemics with thousands of human causalities have been witnessed. The current Covid-19 outbreak represents an unprecedented crisis. In stopping the virus' spread, it is fundamental to have personal protective equipment and disinfected surfaces. Here, the development of a TiO2 nanowires (TiO2NWs) based filter is reported, which it is believed will work extremely well for personal protective equipment (PPE), as well as for a new generation of air conditioners and air purifiers. Its efficiency relies on the photocatalytic generation of high levels of reactive oxygen species (ROS) upon UV illumination, and on a particularly high dielectric constant of TiO2, which is of paramount importance for enhanced wettability by the water droplets carrying the germs. The filter pore sizes can be tuned by processing TiO2NWs into filter paper. The kilogram-scale production capability of TiO2NWs gives credibility to its massive application potentials.
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Most digital information today is encoded in the magnetization of ferromagnetic domains. The demand for ever-increasing storage space fuels continuous research for energy-efficient manipulation of magnetism at smaller and smaller length scales. Writing a bit is usually achieved by rotating the magnetization of domains of the magnetic medium, which relies on effective magnetic fields. An alternative approach is to change the magnetic state directly by acting on the interaction between magnetic moments. Correlated oxides are ideal materials for this because the effects of a small external control parameter are amplified by the electronic correlations. Here, we present a radical method for reversible, light-induced tuning of ferromagnetism at room temperature using a halide perovskite/oxide perovskite heterostructure. We demonstrate that photoinduced charge carriers from the [Formula: see text] photovoltaic perovskite efficiently dope the thin [Formula: see text] film and decrease the magnetization of the ferromagnetic state, allowing rapid rewriting of the magnetic bit. This manipulation could be accomplished at room temperature; hence this opens avenues for magnetooptical memory devices.
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In a seminal paper, Mahan predicted that excitonic bound states can still exist in a semiconductor at electron-hole densities above the insulator-to-metal Mott transition. However, no clear evidence for this exotic quasiparticle, dubbed Mahan exciton, exists to date at room temperature. In this work, we combine ultrafast broadband optical spectroscopy and advanced many-body calculations to reveal that organic-inorganic lead-bromide perovskites host Mahan excitons at room temperature. Persistence of the Wannier exciton peak and the enhancement of the above-bandgap absorption are observed at all achievable photoexcitation densities, well above the Mott density. This is supported by the solution of the semiconductor Bloch equations, which confirms that no sharp transition between the insulating and conductive phase occurs. Our results demonstrate the robustness of the bound states in a regime where exciton dissociation is otherwise expected, and offer promising perspectives in fundamental physics and in room-temperature applications involving high densities of charge carriers.
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We studied the effect of the exposure of human A549 and SH-SY5Y cell lines to aqueous solutions of organic/inorganic halide perovskites CH3NH3PbI3 (MAPbI3) and CH3NH3SnI3 (MASnI3) at the molecular level by using Fourier transform infrared microspectroscopy. We monitored the infrared spectra of some cells over a few days following exposure to the metals and observed the spectroscopic changes dominated by the appearance of a strong band at 1627 cm-1. We used Infrared (IR) mapping to show that this change was associated with the cell itself or the cellular membrane. It is unclear whether the appearance of the 1627 cm-1 band and heavy metal exposure are related by a direct causal relationship. The spectroscopic response of exposure to MAPbI3 and MASnI3 was similar, indicating that it may arise from a general cellular response to stressful environmental conditions. We used 2D correlation spectroscopy (2DCOS) analysis to interpret spectroscopic changes. In a novel application of the method, we demonstrated the viability of 2DCOS for band assignment in spatially resolved spectra. We assigned the 1627 cm-1 band to the accumulation of an abundant amide or amine containing compound, while ruling out other hypotheses. We propose a few tentative assignments to specific biomolecules or classes of biomolecules, although additional biochemical characterization will be necessary to confirm such assignments.
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Compostos de Cálcio/química , Compostos de Cálcio/farmacologia , Iodetos/química , Chumbo/química , Neoplasias Pulmonares/patologia , Metilaminas/química , Neuroblastoma/patologia , Óxidos/química , Óxidos/farmacologia , Titânio/química , Titânio/farmacologia , Sobrevivência Celular , Humanos , Neoplasias Pulmonares/tratamento farmacológico , Neuroblastoma/tratamento farmacológico , Espectrofotometria Infravermelho/métodos , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Compostos de Estanho/química , Células Tumorais CultivadasRESUMO
Homogeneous and stable inorganic coating of SiO2, Al2O3 and TiO2 was obtained on the surface of multiwall carbon nanotubes (MWNTs) by mechanically mixing them with precursor compounds in a planetary ball mill and by subsequent hydrolysis. Detailed studies by means of transmission and scanning electron microscopy revealed that the milling time as well as the number of balls significantly affects the homogeneity of the layer formed. Our results demonstrate that planetary ball milling can be an effective and low-cost process for the production of homogenous coating of oxides on MWNTs in a large-scale.
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The photovoltaic perovskite, methylammonium lead triiodide [CH3NH3PbI3 (MAPbI3)], is one of the most efficient materials for solar energy conversion. Various kinds of chemical and physical modifications have been applied to MAPbI3 towards better understanding of the relation between composition, structure, electronic properties and energy conversion efficiency of this material. Pressure is a particularly useful tool, as it can substantially reduce the interatomic spacing in this relatively soft material and cause significant modifications to the electronic structure. Application of high pressure induces changes in the crystal symmetry up to a threshold level above which it leads to amorphization. Here, a detailed structural study of MAPbI3 at high hydrostatic pressures using Ne and Ar as pressure transmitting media is reported. Single-crystal X-ray diffraction experiments with synchrotron radiation at room temperature in the 0-20â GPa pressure range show that atoms of both gaseous media, Ne and Ar, are gradually incorporated into MAPbI3, thus leading to marked structural changes of the material. Specifically, Ne stabilizes the high-pressure phase of NexMAPbI3 and prevents amorphization up to 20â GPa. After releasing the pressure, the crystal has the composition of Ne0.97MAPbI3, which remains stable under ambient conditions. In contrast, above 2.4â GPa, Ar accelerates an irreversible amorphization. The distinct impacts of Ne and Ar are attributed to differences in their chemical reactivity under pressure inside the restricted space between the PbI6 octahedra.
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For better electrical contacts of potential devices, growth of vertically aligned carbon nanotubes (CNT forests) directly onto conductive substrates is an emerging challenge. Here, we report a systematic study on the CCVD synthesis of carbon nanotube forests on titanium based substrates. As a crucial issue, the effect of the presence of an insulating layer (alumina) on the growing forest was investigated. Other important parameters, such as the influence of water vapor or the Fe-Co catalyst ratio, were also studied during the synthesis. As-prepared CNT forests were characterized by various techniques: scanning and transmission electron microscopies, Raman spectroscopy, spectroscopic ellipsometry. CNT forests grown directly onto the conductive substrate were also tested as electrodes in hybrid halide perovskite photodetectors and found to be effective in detecting light of intensity as low as 3 nW.
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We have investigated the optical absorption of metallic and semiconducting carbon nanotubes/CH3NH3PbI3 micro- and nanowire composites. Upon visible light illumination semiconducting carbon nanotube based samples show a photo-induced doping, originating from the charge carriers created in the perovskite while this kind of change is absent in the composites containing metallic nanotubes, due to their strikingly different electronic structure. The response in the nanotubes shows, beside a fast diffusion of photo-generated charges, a slow component similar to that observed in pristine CH3NH3PbI3 attributed to structural rearrangement, and leading to slight, light induced changes of the optical gap of the perovskite. This charge transfer from the illuminated perovskite confirms that carbon nanotubes (especially semiconducting ones) can form efficient charge-transporting layers in the novel organometallic perovskite based optoelectronic devices.
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Simple, rapid, and inexpensive fabrication of self-cleaning glass surfaces based on wet chemical deposition of H2Ti3O7 (trititanate) and subsequent transformation of it into TiO2 (anatase) nanowires on pristine glass surfaces is reported. Despite the low, 55%, surface coverage, the nanowire roughened glass surface showed self-cleaning properties comparable to much thicker, over 100-nm-thick, TiO2 nanoparticle coated glasses. The superwettable surface showed 12° contact angle. Moreover, ultraviolet (UV) and natural light activated photocatalysis remained effective at enhancing the self-cleaning process in the case of the TiO2 nanowire coated glass. Time-resolved study of the water droplet spread in millisecond time scales revealed that capillary forces induced by the random nanowire network significantly enhance the water sheeting effect of these textured glass surfaces. Time-resolved experiments revealed that the spreading velocity of the droplets were enhanced by 19% for the TiO2 nanowire roughened surface and reached a v0 = 508 mm/s initial spreading speed. Outdoor experiments validated the concept that TiO2 nanowire coated glass possess self-cleaning properties with significantly reduced titania content compared to nanoparticle based films.
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The colloidal stability of titanium oxide nanosheets (TNS) and nanowires (TiONW) was studied in the presence of protamine (natural polyelectrolyte) in aqueous dispersions, where the nanostructures possessed negative net charge, and the protamine was positively charged. Regardless of their shape, similar charging and aggregation behaviors were observed for both TNS and TiONW. Electrophoretic experiments performed at different protamine loadings revealed that the adsorption of protamine led to charge neutralization and charge inversion depending on the polyelectrolyte dose applied. Light scattering measurements indicated unstable dispersions once the surface charge was close to zero or slow aggregation below and above the charge neutralization point with negatively or positively charged nanostructures, respectively. These stability regimes were confirmed by the electron microscopy images taken at different polyelectrolyte loadings. The protamine dose and salt-dependent colloidal stability confirmed the presence of DLVO-type interparticle forces, and no experimental evidence was found for additional interactions (e.g., patch-charge, hydrophobic, or steric forces), which are usually present in similar polyelectrolyte-particle systems. These findings indicate that the polyelectrolyte adsorbs on the TNS and TiONW surfaces in a flat and extended conformation giving rise to the absence of surface heterogeneities. Therefore, protamine is an excellent biocompatible candidate to form smooth surfaces, for instance in multilayers composed of polyelectrolytes and particles to be used in biomedical applications.