Process Intensification for Enhanced Fluoride Removal and Recovery as Calcium Fluoride Using a Fluidized Bed Reactor.

This study explored the feasibility of fluoride removal from simulated semiconductor industry wastewater and its recovery as calcium fluoride using fluidized bed crystallization. The continuous reactor showed the best performance (>90% fluoride removal and >95% crystallization efficiency) at a calcium-to-fluoride ratio of 0.6 within the first 40 days of continuous operation. The resulting particle size increased by more than double during this time, along with a 36% increase in the seed bed height, indicating the deposition of CaF2 onto the silica seed. The SEM-EDX analysis showed the size and shape of the crystals formed, along with the presence of a high amount of Ca-F ions. The purity of the CaF2 crystals was determined to be 91.1% though ICP-OES analysis. Following the continuous experiment, different process improvement strategies were explored. The addition of an excess amount of calcium resulted in the removal of an additional 6% of the fluoride; however, compared to this single-stage process, a two-stage approach was found to be a better strategy to achieve a low effluent concentration of fluoride. The fluoride removal reached 94% with this two-stage approach under the optimum conditions of 4 + 1 h HRT combinations and a [Ca2+]/[F-] ratio of 0.55 and 0.7 for the two reactors, respectively. CFD simulation showed the impact of the inlet diameter, bottom-angle shape, and width-to-height ratio of the reactor on the mixing inside the reactor and the possibility of further improvement in the reactor performance by optimizing the FBR configuration.

Decoding the molecular water structure at complex interfaces through surface-specific spectroscopy of the water bending mode.

The structure of interfacial water determines atmospheric chemistry, wetting properties of materials, and protein folding. The challenge of investigating the properties of specific interfacial water molecules has frequently been confronted using surface-specific sum-frequency generation (SFG) vibrational spectroscopy using the O-H stretch mode. While perfectly suited for the water-air interface, for complex interfaces, a potential complication arises from the contribution of hydroxyl or amine groups of non-water species present at the surface, such as surface hydroxyls on minerals, or O-H and N-H groups contained in proteins. Here, we present a protocol to extract the hydrogen bond strength selectively of interfacial water, through the water bending mode. The bending mode vibrational frequency distribution provides a new avenue for unveiling the hydrogen bonding structure of interfacial water at complex aqueous interfaces. We demonstrate this method for the water-CaF2 and water-protein interfaces. For the former, we show that this method can indeed single out water O-H groups from surface hydroxyls, and that with increasing pH, the hydrogen-bonded network of interfacial water strengthens. Furthermore, we unveil enhanced hydrogen bonding of water, compared to bulk water, at the interface with human serum albumin proteins, a prototypical bio-interface.

Superior temperature sensing of small-sized upconversion nanocrystals for simultaneous bioimaging and enhanced synergetic therapy.

The upconversion nanoparticles (UCNPs) exhibit versatility applications aiming at biological domains for decades on account of superior optical characteristics. Nevertheless, the UCNPs are confronted with tremendous difficulties in biological field owing to large grain size, low fluorescence efficiency, and single function. Herein, the small-sized CaF2: Yb3+/Er3+ UCNPs coated with NaGdF4 shells (activator and inert, UCNPs-RBHA-Pt-PEG) not only burst out strong fluorescence, but also provide prominent diagnosability by taking advantage of magnetic resonance (MR) imaging as well as temperature sensing and inhibiting capability for CT26 tumor tissues based on synergetic therapy modality of photodynamic therapy (PDT) and chemotherapy. Ultimately, the tumor sizes decrease visibly after injected with UCNPs-RBHA-Pt-PEG and simultaneously irradiated with near infrared (NIR) light at low power density (0.35 W/cm2, 6 min). In summary, the small-sized and strong-fluorescent single nanoparticles with multi-functions may provide a valuable enlightenment for diagnosis and treatment of cancer in the future.

Development and Characterization of Bioadhesive Film Embedded with Lignocaine and Calcium Fluoride Nanoparticles.

The formation of biofilm by Streptococcus mutans on the tooth surface is the primary cause of dental caries and periodontal diseases, and fluoride (F) has shown tremendous potential as a therapeutic moiety against these problems. Herein, we report an efficient multi-ingredient bioadhesive film-based delivery system for oral cavity to combat dental problems with an ease of administration. Thiolated chitosan-based bioadhesive film loaded with calcium fluoride nanoparticles (CaF2 NPs) and lignocaine as a continuous reservoir for prolonged delivery was successfully prepared and characterized. The polygonal CaF2 NPs with an average particle size less than 100 nm, PDI 0.253, and + 6.10 mV zeta potential were synthesized and loaded in film. The energy dispersive x-ray (EDX) spectroscopy confirmed the presence 33.13% F content in CaF2 NPs. The characterization of the three film trials for their mechanical strength, bioadhesion, drug release, and permeation enhancement suggested film B as better among the three trials and showed significant outcomes, indicating the potential application of the medicated bioadhesive film. In vitro dissolution studies revealed sustained release pattern of lignocaine and CaF2 NP following Krosmeyer-Peppas model over 8 h. Franz diffusion studies showed the prolonged contact time of film with mucosa that facilitated the transport of CaF2 NPs and lignocaine across the mucosa. Hence, the prepared bioadhesive film-based system showed good potential for better management of dental problems. Graphical Abstract.

Fluoride Binding to Dental Biofilm Bacteria: Synergistic Effect with Calcium Questioned.

It has been suggested that fluoride binding to dental biofilm is enhanced when more bacterial calcium binding sites are available. However, this was only observed at high calcium and fluoride concentrations (i.e., when CaF2 precipitation may have occurred). We assessed fluoride binding to Streptococcus mutans pellets treated with calcium and fluoride at concentrations allowing CaF2 precipitation or not. Increasing calcium concentration resulted in a linear increase (p < 0.01) in fluoride concentration only in the pellets in which CaF2 precipitated. The results suggest that CaF2 precipitation, rather than bacterially bound fluoride, is responsible for the increase in fluoride binding to dental biofilm with the increase in calcium availability.

Ultrasound assisted synthesis of CaF2 :Eu3+ phosphor nanoparticles.

In this work, the optical and structural properties of ultrasonically prepared CaF2 :Eu3+ nanoparticles have been reported. Ultrasonically prepared CaF2 :Eu3+ phosphor shows orange, red emission bands at 591 nm and 612 nm, respectively, when it is excited by 394 light-emitting diode (LED) excitation wavelengths. Further phosphor materials are well characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM) techniques to confirm the phase purity, metal oxygen (MO) bonding and crystallites size of the materials. Here synthesized materials show a tube-like structure under 100 nm resolution and 0.1 mol% is the best doping value of the europium ion (Eu3+ ) in calcium fluoride (CaF2 ) that shows highest intensity when prepared with an ultrasound assisted method.

4-Mercaptobenzoic acid capped terbium(III)-doped CaF2 nanocrystals: a fluorescent probe for nitroaromatic pollutants.

The authors report on an energy transfer based fluorometric approach for the detection of nitroaromatic pollutants. This is achieved using 4-mercaptobenzoic acid (4-MBA)-capped CaF2:Tb3+ nanocrystals that were synthesized by a microwave procedure. 4-MBA acts as both a capping agent and a sensitizer for the Tb3+ ions in CaF2 host matrix. This approach is different from the earlier studies where Ce3+ is generally used as the sensitizer for the Ln3+ ions. The use of capping ligand as sensitizer has the feature that binding of nitroaromatics directly to the sensitizer can alter the energy transfer efficiency between the sensitizer and the Tb3+ ions. The fluorescent nanocrystal probe doped with 2% of Tb3+ displays green emission with a peak at 542 nm if photoexcited at 311 nm. The emission is quenched if the nanocrystals are exposed to nitroaromatic compounds such as 4-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol (picric acid), 4-nitrotoluene, 2,4-dinitrotoluene and 2,4,6-trinitrotoluene. These analytes also cause a (longwave/shortwave) shift in the excitation maxima which helps in identifying the individual nitroaromatic compound using single nanoprobe. The respective detection limits (by applying the 3σ/K criterion) are 0.86 µM, 0.83 µM, 0.78 µM, 0.36 µM, 1.5 µM, and 1.96 µM. Graphical abstract Schematic illustration of the use of 4-mercaptobenzoic acid (MBA)-capped CaF2:Tb3+ nanocrystals as a fluorescent nanoprobe for the detection of nitroaromatic analytes. The Tb3+ ions show strong green fluorescence via 4-MBA-induced ligand sensitization. The specific π interaction between 4-MBA capped CaF2 nanocrystals and nitroaromatics leads to reduction in the fluorescence intensity by inhibiting the energy transfer from 4-MBA to Tb3+ ion in CaF2 nanocrystals.

Calcium-based biomaterials for diagnosis, treatment, and theranostics.

Calcium-based (CaXs) biomaterials including calcium phosphates, calcium carbonates, calcium silicate and calcium fluoride have been widely utilized in the biomedical field owing to their excellent biocompatibility and biodegradability. In recent years, CaXs biomaterials have been strategically integrated with imaging contrast agents and therapeutic agents for various molecular imaging modalities including fluorescence imaging, magnetic resonance imaging, ultrasound imaging or multimodal imaging, as well as for various therapeutic approaches including chemotherapy, gene therapy, hyperthermia therapy, photodynamic therapy, radiation therapy, or combination therapy, even imaging-guided therapy. Compared with other inorganic biomaterials such as silica-, carbon-, and gold-based biomaterials, CaXs biomaterials can dissolve into nontoxic ions and participate in the normal metabolism of organisms. Thus, they offer safer clinical solutions for disease theranostics. This review focuses on the state-of-the-art progress in CaXs biomaterials, which covers from their categories, characteristics and preparation methods to their bioapplications including diagnosis, treatment, and theranostics. Moreover, the current trends and key problems as well as the future prospects and challenges of CaXs biomaterials are also discussed at the end.

Static Solid Relaxation Ordered Spectroscopy: SS-ROSY.

A two-dimensional pulse sequence is introduced for correlating nuclear magnetic resonance anisotropic chemical shifts to a relaxation time (e.g., T1) in solids under static conditions. The sequence begins with a preparatory stage for measuring relaxation times, and is followed by a multiple pulse sequence for homonuclear dipolar decoupling. Data analysis involves the use of Fourier transform, followed by a one-dimensional inverse Laplace transform for each frequency index. Experimental results acquired on solid samples demonstrate the general approach, and additional variations involving heteronuclear decoupling and magic angle spinning are discussed.

On the Morphology of Group II Metal Fluoride Nanocrystals at Finite Temperature and Partial Pressure of HF.

We have investigated the bulk and surface properties of the group II metal fluorides CaF 2 , SrF 2 and BaF 2 using periodic density functional theory (DFT) calculations and surface thermodynamics. Our bulk results show that the best agreement with experiment is achieved with the B3LYP and PBE functionals. We determined the relative importance of the low index surfaces in vacuum and found that an fluoride microcrystal exposes only the (111) surface in which the undercoordinated cations are sevenfold coordinated. With methods of ab initio surface thermodynamics, we analyzed the stability of different surfaces under hydrogen fluoride (HF) pressure and determined the presumable shape of the crystals with respect to different HF concentrations and temperatures. In the case of CaF 2 and SrF 2 , the calculated shapes of the crystals agree well with TEM images of fluorolytic sol-gel synthesized nanocrystals at room temperature and high HF concentration.

Removal of ammonium and heavy metals by cost-effective zeolite synthesized from waste quartz sand and calcium fluoride sludge.

This study focuses on the effectiveness of zeolite (10% CF-Z [0.5]) hydrothermally synthesized from waste quartz sand and calcium fluoride (CF) for ammonium ion and heavy metal removal. Zeolite was characterized through powder X-ray diffraction, Fourier-transform infrared spectroscopy, micromeritics N2 adsorption/desorption analysis, and field emission scanning electron microscopy. The effects of CF addition, Si/Al ratio, initial ammonium concentration, solution pH, and temperature on the adsorption of ammonium on 10% CF-Z (0.5) were further examined. Results showed that 10% CF-Z (0.5) was a single-phase zeolite A with cubic-shaped crystals and 10% CF-Z (0.5) efficiently adsorbs ammonium and heavy metals. For instance, 91% ammonium (10 mg L-1) and 93% lead (10 mg L-1) are removed. The adsorption isotherm, kinetics, and thermodynamics of ammonium adsorption on 10% CF-Z (0.5) were also theoretically analyzed. The adsorption isotherm of ammonium and lead on 10% CF-Z (0.5) in single systems indicated that Freundlich model provides the best fit for the equilibrium data, whereas pseudo-second-order model best describes the adsorption kinetics. The adsorption degree of ions on 10% CF-Z (0.5) in mixed systems exhibits the following pattern: lead > ammonium > cadmium > chromium.

Highly aqueous soluble CaF2:Ce/Tb nanocrystals: effect of surface functionalization on structural, optical band gap, and photoluminescence properties.

The design of nanostructured materials with highly stable water-dispersion and luminescence efficiency is an important concern in nanotechnology and nanomedicine. In this paper, we described the synthesis and distinct surface modification on the morphological structure and optical (optical absorption, band gap energy, excitation, emission, decay time, etc.) properties of highly crystalline water-dispersible CaF2:Ce/Tb nanocrystals (core-nanocrystals). The epitaxial growth of inert CaF2 and silica shell, respectively, on their surface forming as CaF2:Ce/Tb@CaF2 (core/shell) and CaF2:Ce/Tb@CaF2@SiO2 (core/shell/SiO2) nanoarchitecture. X-ray diffraction and transmission electron microscope image shows that the nanocrystals were in irregular spherical phase, highly crystalline (~20 nm) with narrow size distribution. The core/shell nanocrystals confirm that the surface coating is responsible in the change of symmetrical nanostructure, which was determined from the band gap energy and luminescent properties. It was found that an inert inorganic shell formation effectively enhances the luminescence efficiency and silica shell makes the nanocrystals highly water-dispersible. In addition, Ce3+/Tb3+-co-doped CaF2 nanocrystals show efficient energy transfer from Ce3+ to Tb3+ ion and strong green luminescence of Tb3+ ion at 541 nm(5D4→7F5). Luminescence decay curves of core and core/shell nanocrystals were fitted using mono and biexponential equations, and R 2 regression coefficient criteria were used to discriminate the goodness of the fitted model. The lifetime values for the core/shell nanocrystals are higher than core-nanocrystals. Considering the high stable water-dispersion and intensive luminescence emission in the visible region, these luminescent core/shell nanocrystals could be potential candidates for luminescent bio-imaging, optical bio-probe, displays, staining, and multianalyte optical sensing. A newly designed CaF2:Ce/Tb nanoparticles via metal complex decomposition rout shows high dispersibility in aqueous solvents with enhanced photoluminescence. The epitaxial growth of inert CaF2 shell and further amorphous silica, respectively, enhanced their optical and luminescence properties, which is highly usable for luminescent biolabeling, and optical bioprobe etc.

Assessing the Influence of Calcium Fluoride on Pyrite Electrochemical Dissolution and Mine Drainage pH.

We investigated the influence of dissolved calcium fluoride, CaF(aq), on the electrochemical dissolution of pyrite and the corresponding environmental effects on acid mine drainage (AMD). The experimental results showed that CaF(aq) promotes pyrite electrochemical dissolution. When the CaF(aq) concentration increased from 0 to 10 mg L up to saturation, the promoting efficiency was 15.80 and 57.25%, respectively. The reason for this phenomenon is that F and Fe form FeF, and at a higher scan potential, F and Fe form the ion complex FeF. The mechanisms include: (i) the decreasing charge transfer resistance at the double layer due to the iron fluorine complex formation; and (ii) the decreasing passivation resistance at the cover layer due to the strong penetration of F ions through it into the double layer. Although the hydrolysis reaction of F in solution could increase the pH value of mine drainage, the AMD was significantly aggravated because CaF(aq) promoted the pyrite electrochemical dissolution.

Effects of different pre-treatment methods on the shear bond strength of orthodontic brackets to demineralized enamel.

OBJECTIVE: To compare the effects of different treatment methods used for the enamel damage, on the shear bond strength (SBS) and fracture mode of orthodontic brackets. MATERIALS AND METHODS: Freshly-extracted 140 premolars were randomly allocated to seven groups: Group I was considered as the control of other groups. The remaining groups were exposed to demineralization. In group II, brackets were directly bonded to the demineralized enamel surface. CPP-ACP paste (GC Tooth Mousse), fluoride varnish (Bifluorid 12), microabrasion with a mixture prepared with 18% hydrochloric acid and fine pumice powder, microabrasion with an agent (Opalustre) and resin infiltrant (Icon®) were applied in Groups III, IV, V, VI and VII, respectively. The specimens were tested for SBS and bond failures were scored according to the Adhesive Remnant Index (ARI). Analysis of variance and Tukey tests were used to compare the SBS of the groups. ARI scores were compared with G-test. The statistical significance was set at p < 0.05 level. RESULTS: Statistically significant differences were found among seven groups (F = 191.697; p < 0.001). The SBSs of groups I (mean = 18.8 ± 2.0 MPa) and VII (mean = 19.1 ± 1.4 MPa) were significantly higher than the other groups. No statistically significant difference was found between groups IV (mean = 11.5 ± 1.2 MPa) and V (mean = 12.6 ± 1.5 MPa). The differences in ARI scores of the groups were statistically significant (p < 0.01). CONCLUSIONS: All demineralization treatment methods improve bonding to demineralized enamel. Resin infiltrant application after demineralization showed similar bond strength values as intact enamel.

Generation of Kerr combs centered at 4.5 µm in crystalline microresonators pumped with quantum-cascade lasers.

We report on the generation of mid-infrared Kerr frequency combs in high-finesse CaF2 and MgF2 whispering-gallery-mode resonators pumped with continuous-wave room-temperature quantum cascade lasers. The combs were centered at 4.5 µm, the longest wavelength to date. A frequency comb wider than one half of an octave was demonstrated when approximately 20 mW of pump power was coupled to an MgF2 resonator characterized with quality factor exceeding 10(8).

Combining total internal reflection sum frequency spectroscopy spectral imaging and confocal fluorescence microscopy.

Understanding surface and interfacial lateral organization in material and biological systems is critical in nearly every field of science. The continued development of tools and techniques viable for elucidation of interfacial and surface information is therefore necessary to address new questions and further current investigations. Sum frequency spectroscopy (SFS) is a label-free, nonlinear optical technique with inherent surface specificity that can yield critical organizational information on interfacial species. Unfortunately, SFS provides no spatial information on a surface; small scale heterogeneities that may exist are averaged over the large areas typically probed. Over the past decade, this has begun to be addressed with the advent of SFS microscopy. Here we detail the construction and function of a total internal reflection (TIR) SFS spectral and confocal fluorescence imaging microscope directly amenable to surface investigations. This instrument combines, for the first time, sample scanning TIR-SFS imaging with confocal fluorescence microscopy.

Modification of luminescence spectra of CaF2:Eu2+.

CaF2:Eu(2+) is a well known phosphor having efficient excitation in the near ultraviolet (NUV) range. Phosphors with NUV excitation are required in newly emerging applications such as photoluminescence liquid crystal displays (PLLCD), solid-state lighting (SSL), and down-conversion for solar cells. However, emission of CaF2:Eu(2+) is around 424 nm. Eye sensitivity drops considerably at these wavelengths. It is thus not useful for display applications for which emission in one of the primary colours (blue - 450 nm, green - 540 nm or red - 610 nm) is required. Efforts were made to modify the Photoluminescence (PL) spectra of CaF2:Eu(2+) to meet these requirements using co-dopants. A Ca0.49 Sr0.50 Eu0.01 F2 phosphor showing better colour coordinates and having an emission maximum around 440 nm was discovered during these studies.

Influence of the Relative Enamel Abrasivity (REA) of Toothpastes on the Uptake of KOH-soluble and Structurally Bound Fluoride.

PURPOSE: To determine the influence of the relative enamel abrasivity (REA) of fluoridated toothpaste on the uptake of KOH-soluble and structurally bound fluoride into enamel. MATERIALS AND METHODS: Bovine enamel samples were randomly allocated to 6 groups (n=36 per group). Groups A to C were treated with sodium fluoride (NaF) toothpastes and groups D to F with amine fluoride (AmF) toothpastes (1500 ppm F each). The REA in groups A and D was 2, in groups B and E it was 6 and in groups C and F it was 9. Twice a day, 18 samples of each group were immersed for 2 min in a slurry (toothpaste:artificial saliva=1:3), while the remaining samples were brushed with the respective slurry (2.5 N force; 60 strokes/min; 2 min). All samples were stored at 37°C and 100% humidity. After five days, the amount of KOH-soluble and structurally bound fluoride was determined and statistically compared by Scheffe's post-hoc tests. RESULTS: REA value and mode of application (immersion or brushing) had no significant influence on the amount of either kind of fluoride from NaF toothpastes. Only for the NaF toothpaste with REA 6 was the amount of KOH-soluble fluoride significantly higher after brushing. With AmF toothpastes, KOH-soluble and structurally bound fluoride concentrations were significantly higher when the samples were brushed. Furthermore, in the REA-2 group, the amounts of KOH-soluble fluoride (brushed or immersed) and structurally bound fluoride (brushed) were significantly higher than in the other groups. CONCLUSION: The REA dependency of KOH-soluble and structurally bound fluoride was found only for the AmF toothpastes. Using AmF toothpaste, the mode of application influenced the uptake of KOH-soluble and structurally bound fluoride into enamel.

Improved multiphoton ultraviolet upconversion photoluminescence in ultrasmall core-shell nanocrystals.

Near-infrared to ultraviolet multiphoton upconversion photoluminescence in ultrasmall Tm3+/Yb3+-codoped CaF2 nanocrystals (∼6.7 nm in size) was observed and further significantly enhanced by growing an active shell of NaYF4:Yb3+. Owing to the active shell, the lanthanide emitters inside the core are effectively prevented from the surface quenchers, and the excitation energy is absorbed more efficiently via the additional luminescence sensitizer Yb3+ embedded in the shell. The details of underlying physics were investigated and discussed. The results present a good ultrasmall luminescent material system for achieving efficient multiphoton upconversion, which shows great potential in versatile industrial and biological applications.

Study on the methylene blue adsorption from wastewaters by pore-expanded calcium fluoride sludge adsorbent.

The adsorption of methylene blue (MB) onto pore-expanded calcium fluoride sludge (ECF) by the batch adsorption technique was investigated. The results showed that the adsorption capacity increased with increasing MB concentration but decreased as pH was increased. In order to investigate the adsorption mechanisms, three simplified isotherm models and kinetic models were used in this study. The best-fit adsorption isotherm was achieved with the Temkin model. Furthermore, the pseudo-second-order kinetic model agreed very well with the dynamical behavior for the adsorption of MB onto ECF. Thermodynamic studies revealed that the adsorption process of MB onto ECF was spontaneous and exothermic. The results indicated that ECF adsorbed MB efficiently and could be used as a waste adsorbent for the removal of cationic dyes in wastewater treatment.