High-Performance Photocatalytic Reduction of Nitrogen to Ammonia Driven by Oxygen Vacancy and Ferroelectric Polarization Field of SrBi4 Ti4 O15 Nanosheets.

Photo-responsive semiconductors can facilitate nitrogen activation and ammonia production, but the high recombination rate of photogenerated carriers represents a significant barrier. Ferroelectric photocatalysts show great promise in overcoming this challenge. Herein, by adopting a low-temperature hydrothermal procedure with varying concentrations of glyoxal as the reducing agent, oxygen vacancies (Vo) are effectively produced on the surface of ferroelectric SrBi4 Ti4 O15 (SBTO) nanosheets, which leads to a considerable increase in photocatalytic activity toward nitrogen fixation under simulated solar light with an ammonia production rate of 53.41 µmol g-1 h-1 , without the need of sacrificial agents or photosensitizers. This is ascribed to oxygen vacancies that markedly enhance the self-polarization and internal electric field of ferroelectric SBTO, and hence, facilitate the separation of photogenerated charge carriers and light trapping as well as N2 adsorption and activation, as compared to pristine SBTO. Consistent results are obtained in theoretical studies. Results from this study highlight the significance of surface oxygen vacancies in enhancing the performance of photocatalytic nitrogen fixation by ferroelectric catalysts.

Stable Cuprous Hydroxide Nanostructures by Organic Ligand Functionalization.

Copper compounds have been extensively investigated for diverse applications. However, studies of cuprous hydroxide (CuOH) have been scarce due to structural metastability. Herein, a facile, wet-chemistry procedure is reported for the preparation of stable CuOH nanostructures via deliberate functionalization with select organic ligands, such as acetylene and mercapto derivatives. The resulting nanostructures are found to exhibit a nanoribbon morphology consisting of small nanocrystals embedded within a largely amorphous nanosheet-like scaffold. The acetylene derivatives are found to anchor onto the CuOH forming CuC linkages, whereas CuS interfacial bonds are formed with the mercapto ligands. Effective electronic coupling occurs at the ligand-core interface in the former, in contrast to mostly non-conjugated interfacial bonds in the latter, as manifested in spectroscopic measurements and confirmed in theoretical studies based on first principles calculations. Notably, the acetylene-capped CuOH nanostructures exhibit markedly enhanced photodynamic activity in the inhibition of bacteria growth, as compared to the mercapto-capped counterparts due to a reduced material bandgap and effective photocatalytic generation of reactive oxygen species. Results from this study demonstrate that deliberate structural engineering with select organic ligands is an effective strategy in the stabilization and functionalization of CuOH nanostructures, a critical first step in exploring their diverse applications.

Dehydration imaging of dental fluorosis at 1950 nm.

Dental fluorosis is an increasing problem in the U.S. due to excessive exposure to fluoride from the environment. Fluorosis causes hypomineralization of the enamel during tooth development and mild fluorosis is visible as faint white lines on the tooth surface while the most severe fluorosis can result in pitted surfaces. It is difficult to differentiate lesions due to fluorosis from those due to caries. Dental fluorosis appears with extremely high contrast at short wavelength infrared (SWIR) wavelengths of 1450 and 1960 nm coincident with higher water absorption. In this study reflectance measurements at 1450 and 1950 nm were used to monitor the dehydration dynamics of lesions due to fluorosis on extracted teeth. The dehydration dynamics were compared with the lesion structure that was measured with microCT. Sixteen extracted teeth with suspected fluorosis were imaged and microCT showed that the mean surface zone thickness was 118 ± 30 µm and the lesion depth was 284 ± 105 µm for the areas of fluorosis investigated. The dehydration dynamics of lesions due to fluorosis appeared most similar to those of arrested caries lesions. There was no significant correlation (P >0.05) of the intensity change and rate of the intensity change at 1450 or 1950 nm with either the lesion surface zone thickness or the lesion depth.

Use of SWIR dehydration and OCT to assess the complete arrest of simulated incipient caries lesions.

Previous studies have shown that optical coherence tomography (OCT) can be used to show the formation of a transparent surface zone on caries lesions indicative of remineralization. Studies have also shown that monitoring changes in the diffuse reflectivity of caries lesions during drying with air can be used to assess lesion activity and that the largest changes occur at SWIR wavelengths coincident with high water absorption at 1450 and 1950 nm. The purpose of this study was to determine when remineralization has occurred by monitoring changes in SWIR reflectance measurements and OCT images of simulated lesions over an extended time period during exposure to a remineralization solution. Eight bovine enamel surfaces each with two treatment windows were exposed to a pH cycling regimen to produce simulated lesions 50-100 µm deep. OCT at 1310 nm was used to image the samples at each time point. An extended range tungsten halogen lamp with a 1450 nm band pass filter and a broadband amplified spontaneous emission source centered near the peak of the water-absorption band at 1950 nm were used as light sources. An extended range InGaAs camera (1000-2340 nm) was used to acquire reflected light images as the samples were dried with air. After 32 days of exposure to the remineralization solution there were no further changes to the samples suggesting they had been completely arrested.

Caries inhibition of simulated active caries lesions with CO2 laser irradiation and fluoride.

It has been well established that CO2 laser irradiation can be used to transform the mineral phase of dental enamel to make it more resistant to acid dissolution. The purpose of this study was to investigate if carbon dioxide laser irradiation and topical fluoride can be used to treat incipient caries lesions to inhibit further progression, i.e. treat active lesion surfaces as opposed to sound surfaces prior to subjecting them to an acid challenge. Simulated active caries lesions were produced on twenty eight bovine enamel samples using a pH cycling model and those surfaces were irradiated by a 9.4 µm CO2 laser and treated with topical fluoride. Changes in the surface morphology, acid resistance, and permeability were measured using digital microscopy, optical coherence tomography (OCT), and SWIR reflectance surface dehydration rate measurements at 1950 nm after exposure to a further acid challenge. There was a significant reduction (P < 0.05) of further lesion progression for lesion windows treated with CO2 laser irradiation followed by the application of an acidulated phosphate fluoride gel compared to the untreated lesion windows on each sample. Treatment by laser irradiation alone was not effective. The degree of lesion inhibition was not as high as has been previously observed for laser irradiated sound enamel surfaces exposed to an acid challenge.

High-Efficiency Photodynamic Antibacterial Activity of NH2-MIL-101(Fe)@MoS2/ZnO Ternary Composites.

Bacterial infections are a serious threat to human health, and the development of effective antibacterial agents represents a critical solution. In this study, NH2-MIL-101(Fe)@MoS2/ZnO ternary nanocomposites are successfully prepared by a facile wet-chemistry procedure, where MoS2 nanosheets are grown onto the MIL-101 scaffold forming a flower-like morphology with ZnO nanoparticles deposited onto the surface. The ternary composites exhibit a remarkable sterilization performance under visible light irradiation toward both Gram-negative and Gram-positive bacteria, eliminating 98.6% of Escherichia coli and 90% of Staphylococcus aureus after exposure to visible light for 30 min, a performance markedly better than that with NH2-MIL-101(Fe)@MoS2 binary composites and even more so than MoS2 nanosheets alone. This is ascribed to the unique electronic band structure of the composites, where the separation of the photogenerated carriers is likely facilitated by the S-scheme mechanism in the NH2-MIL-101(Fe)@MoS2 binary composites and further enhanced by the formation of a p-n heterojunction between MoS2 and ZnO in the ternary composites. This interfacial charge transfer boosts the effective production of superoxide radicals by the reduction of oxygen, and the disproportionation reaction with water leads to the formation of hydroxy radicals, as attested in spectroscopic and microscopic measurements. Results from this study highlight the significance of structural engineering of nanocomposites in the manipulation of the electronic band structure and hence the photodynamic activity.

High contrast reflectance imaging at 1950 nm for the assessment of lesion activity on extracted teeth.

Changes in the reflectivity of lesions on the proximal surfaces of extracted human teeth were measured at SWIR wavelengths from 1300-2000 nm as they were dried with air to assess lesion activity. An extended range tungsten-halogen lamp with bandpass filters of varying wavelength (bandwidth) 1300 nm (90), 1460 nm (85), 1535 nm (80), and 1675 nm (90) along with a broadband ASE source centered near the peak of the water-absorption band at 1950-nm were used as light sources and an extended range InGaAs camera (1000-2340 nm) was used to acquire reflected light images as the samples were dried with air. MicroCT images were used as a gold standard for comparison. SWIR light at 1950 nm yields extremely high contrast of demineralization and appears to be the optimum wavelength for the assessment of lesion activity on tooth coronal surfaces.

Dynamic SWIR imaging near the 1950-nm water absorption band for caries lesion diagnosis.

SIGNIFICANCE: It is not sufficient to detect caries lesions on tooth surfaces; it is also necessary to measure the activity of the lesions to determine if intervention is needed. Changes in the reflectivity of lesion areas during dehydration with forced air at short wavelength infrared (SWIR) wavelengths can be used to assess lesion activity since these changes represent the evaporation dynamics of water from the lesion. AIM: The aim of this study is to develop new optical methods for assessing lesion activity on tooth surfaces utilizing the strong water absorption band near 1950-nm. APPROACH: The time-resolved reflectivity of 20 active and arrested caries lesions on the surfaces of human extracted teeth was monitored at 1300 to 2000 nm using broadband light sources and an extended range InGaAs camera during drying with air. RESULTS: Multiple parameters representing the rate of change of the lesion reflectivity correlated with the presence of a highly mineralized outer surface zone indicative of lesion arrest measured with x-ray microtomography (microCT). Performance at 1950-nm was higher than for other wavelengths. CONCLUSIONS: This study demonstrates that SWIR imaging near 1950-nm has great potential for the assessment of lesion activity.

High contrast imaging of dental fluorosis in the short wavelength infrared.

Dental fluorosis is an increasing problem due to over exposure to fluoride from the environment. Fluorosis causes hypomineralization of the enamel during tooth development and mild fluorosis is visible as faint white lines on the tooth surface while the most severe fluorosis can result in pitted surfaces. It is difficult to quantify the severity of mild to moderate fluorosis and assessments are limited to subjective visual examinations. Dental fluorosis appears with very high contrast at short wavelength infrared (SWIR) wavelengths beyond 1400 nm and we hypothesize that these wavelengths may be better suited for detecting mild fluorosis and for estimating the severity on tooth surfaces. In this study, the contrast of fluorosis of varying severity on extracted human permanent teeth was measured at SWIR wavelengths ranging from 1300 to 2150 nm using an extended range of InGaAs camera and broadband light sources. The contrast was also measured in the visible range and with quantitative light-induced fluorescence (QLF) for comparison. The depth of hypomineralization and the integrated reflectivity were also measured with cross-polarization optical coherence tomography. The contrast of hypomineralization is significantly higher (P < 0.05) at 1460 and 1950 nm wavelengths than for the visible, fluorescence or other SWIR wavelengths from 1300 to 2150 nm. The highest correlation of the contrast with the depth of hypomineralization measured with cross-polarization-optical coherence tomography (CP-OCT) was at 1950 nm. This SWIR in vitro imaging study exploring wavelengths beyond 1400 nm has shown that hypomineralization on tooth surfaces can be viewed with extremely high contrast at SWIR wavelengths from 1460 to 2000 nm and that SWIR imaging has great potential for monitoring hypomineralization on tooth surfaces. New clinical methods are needed for the measurement of fluorosis that are valid, reliable, and feasible for surveillance at the community level. In addition, methods are needed for the quantitative assessment of fluorosis in vivo.