Recovery of aluminum oxide and iron oxide from aluminum electrolysis iron-rich cover material and preparation of aluminum fluoride.

In aluminum electrolysis, the iron-rich cover material is formed on the cover material and the steel rod connecting the carbon anode. Due to the high iron content in the iron-rich cover material, it differs from traditional cover material and thus requires harmless recycling and treatment. A process was proposed and used in this study to recovery F, Al, and Fe elements from the iron-rich cover material. This process involved aluminum sulfate solution leaching for fluorine recovery and alkali-acid synergistic leaching for α-Al2O3 and Fe2O3 recovery were obtained. The optimal leaching rates for F, Na, Ca, Fe, and Si were 93.92, 96.25, 94.53, 4.48, and 28.87%, respectively. The leaching solution and leaching residue were obtained. The leaching solution was neutralized to obtain the aluminum hydroxide fluoride hydrate (AHFH, AlF1.5(OH)1.5·(H2O)0.375). AHFH was calcined to form a mixture of AlF3 and Al2O3 with a purity of 96.14%. The overall recovery rate of F in the entire process was 92.36%. Additionally, the leaching residue was sequentially leached with alkali and acid to obtain the acid leach residue α-Al2O3. The pH of the acid-leached solution was adjusted to produce a black-brown precipitate, which was converted to Fe2O3 under a high-temperature calcination, and the recovery rate of Fe in the whole process was 94.54%. Therefore, this study provides a new method for recovering F, Al, and Fe in iron-rich cover material, enabling the utilization of aluminum hazardous waste sources.

Preparation of alumina-supported Fe-Al-La composite for fluoride removal from an aqueous matrix.

Using groundwater for human consumption is an alternative for places with no nearby surface water resources. Fluoride is commonly found in groundwater, and the consumption of this water for a prolonged time in concentrations that exceed established limits by WHO and Brazilian legislation on water potability (1.5 mg L-1) can cause harmful problems to human health. For this reason, fluoride removal is an important step before water consumption. In this work, activated alumina was impregnated with Fe-Al-La composite and employed for the first time as an adsorbent for fluoride removal from an aqueous environment. XRD, SEM/EDS, FT-IR, and point of zero charge were used to characterize the prepared adsorbent. The adsorptive performance of adsorbent material was investigated by employing a 23-central composite design (CCD), and the obtained experimental conditions were pH = 6.5 and adsorbent dosage = 3.0 g L-1. A maximum adsorption capacity of 8.17 mg g-1 at 298 K and pH = 6.5 was achieved by Langmuir isotherm to describe the adsorption. The kinetic model that better described experimental data was Avrami, with the kav parameter increasing with the initial concentration from 0.076 to 0.231 (min-1)nav. The nature of adsorption was found to be homogeneous, and it occurs in a monolayer. The fluoride removal performance for the prepared adsorbent was higher than granular activated alumina, showing that supporting Fe-Al-La at the alumina surface increased its fluoride adsorption capacity from 16 to 42% at the same experimental conditions. Finally, the influence of co-existing ions Cl-, SO42-, and NO3- was evaluated in fluoride adsorption, and the material presented great selectivity to fluoride. Thus, Fe-Al-La/AA adsorbent is a promising material for fluoride removal from water.

Resin-modified glass ionomer enriched with BIOGLASS: Ion-release, bioactivity and antibacterial effect.

Developing dental materials for the prevention of remineralization or demineralization is important for high-risk caries patients. This study aimed to evaluate the physicochemical and microbiological effects of adding 45S5 bioglass to resin-modified glass ionomer cement (RMGIC). Samples belonged to the following groups: GIC: conventional glass ionomer cement (Vitro Fil), RMGIC: resin-modified GIC (Vitro Fil LC), and RMGIC/45S5: RMGIC with 10% (wt %) of 45S5. Changes in pH and release of fluoride, calcium, and phosphorus ions under acidic (pH 4) and neutral (pH 7) pH conditions were evaluated. Antibacterial activity was verified based on colony-forming units. Material sorption and solubility were analyzed after bacterial exposure. After 28 days, the bioactivity of the materials was evaluated using scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS). Analysis of variance, post hoc Scheffe, and Tukey (α = 0.05) tests were employed for statistical analysis. RMGIC/45S5 showed higher alkalization activity, calcium release at pH 4 and 7, and sorption than GIC and RMGIC (p < .05). Release of phosphorus and fluoride at pH 4 and 7 was higher for GIC than that for RMGIC and RMGIC/45S5 (p < .05). RMGIC/45S5 showed higher values than RMGIC (p < .05). However, antibacterial activity did not differ among the groups. Precipitates of calcium and phosphorus were visualized in RMGIC/45S5 samples via SEM/EDS. These results indicate that the RMGIC/45S5 promotes alkalization and increases the release of calcium, phosphorus, and fluoride ions, resulting in precipitate deposition rich in calcium and phosphorus, thereby being a promising option to improve the bioactivity of RMGIC.

Mechanism-Driven Development of Group 10 Metal-Catalyzed Decarbonylative Coupling Reactions.

Transition-metal-catalyzed cross-coupling reactions are widely used in both academia and industry for the construction of carbon-carbon and carbon-heteroatom bonds. The vast majority of cross-coupling reactions utilize aryl (pseudo)halides as the electrophilic coupling partner. Carboxylic acid derivatives (RC(O)X) represent a complementary class of electrophiles that can engage in decarbonylative couplings to produce analogous products. This decarbonylative approach offers the advantage that RC(O)X are abundant and inexpensive. In addition, decarbonylative coupling enables both intramolecular (between R and X of the carboxylic acid derivative) as well as intermolecular bond-forming reactions (in which an exogeneous nucleophile is coupled with the R group derived from RC(O)X). In these intermolecular reactions, the X-substituent on the carboxylic acid can be tuned to facilitate both oxidative addition and transmetalation, thus eliminating the need for an exogeneous base. This Account details our group's development of a diverse variety of base-free decarbonylative coupling reactions catalyzed by group 10 metals. Furthermore, it highlights how catalyst design can be guided by stoichiometric organometallic studies of these systems.Our early studies focused on intramolecular decarbonylative couplings that transform RC(O)X to the corresponding R-X with extrusion of CO. We first identified Pd and Ni monodentate phosphine catalysts that convert aryl thioesters (ArC(O)SR) to the corresponding thioethers (ArSR). We next expanded this reactivity to fluoroalkyl thioesters, using readily available fluoroalkyl carboxylic acids as the fluoroalkyl (RF) source. A Ni-phosphinoferrocene catalyst proved optimal, and the large bite angle bidentate ligand was necessary to promote the challenging RF-S bond-forming reductive elimination step.We next pursued intramolecular decarbonylative couplings of aroyl halides. Palladium-based catalysts bearing dialkylbiaryl ligands (e.g., BrettPhos) were identified as optimal for converting aroyl chlorides (ArC(O)Cl) to aryl chlorides (ArCl). These ligands were selected based on their ability to facilitate the key C-Cl bond-forming reductive elimination step of the catalytic cycle. In contrast, all attempts to convert aroyl fluorides [ArC(O)F)] to aryl fluorides (ArF) were unsuccessful with either Pd- or Ni-based catalysts. Organometallic studies of the Ni-system show that C(O)-F oxidative addition and CO deinsertion proceed smoothly, but the resulting nickel(II) aryl fluoride intermediate fails to undergo C-F bond-forming reductive elimination.In contrast to its inertness to reductive elimination, this nickel(II) aryl fluoride proved highly reactive toward transmetalation. The fluoride ligand serves as an internal base, such that no additional base is required. We leveraged this "transmetalation active" intermediate to achieve base-free Ni-catalyzed intermolecular decarbonylative coupling reactions between aroyl fluorides and boron reagents to access both biaryl and aryl-boronate ester products. By tuning the electrophile, transmetalating reagent, and catalyst, this same approach also proved applicable to base-free intermolecular decarbonylative fluoroalkylation (between difluoromethylacetyl fluoride and arylboronate esters) and aryl amination (between phenol esters and silyl amines).Moving forward, a key goal is to identify catalyst systems that enable more challenging bond constructions via this manifold. In addition, CO inhibition remains a major issue leading to the requirement for high temperatures and high catalyst loadings. Identifying catalysts that are resistant to CO binding and/or approaches to remove CO under mild conditions will be critical for making these reactions more practical and scalable.

Pr3+ doped NaYF4 and LiYF4 nanocrystals combining visible-to-UVC upconversion and NIR-to-NIR-II downconversion luminescence emissions for biomedical applications.

Lanthanide-doped fluoride nanocrystals (NCs) are known to exhibit unique optical properties, such as upconversion and downconversion luminescence (UCL and DCL), which can be employed for various applications. In this work, we demonstrate that by doping praseodymium(III) and ytterbium(III) ions (Pr3+ and Yb3+) into a nanosized fluoride matrix (i.e. NaYF4 and LiYF4), it is possible to combine their UCL and DCL properties that can be concurrently used for biomedical applications. In particular, the emissive modes combined in a single nanoparticle co-doped with Pr3+ and Yb3+ include DCL emission (excited at 980 nm and peaked at 1320 nm), which can be used for near infrared (NIR) DCL bioimaging in the NIR-II window of biological tissue transparency (∼1000-1350 nm) and UCL emission (excited at 447 nm and peaked at 275 nm) that can be employed for germicide action (via irradiation by light in the UVC range). A possibility of the latter was demonstrated by the denaturation of double-stranded DNA (dsDNA) into single-stranded ones that was caused by the UVC UCL emission from the NCs under 447 nm irradiation; it was evidenced by the hyperchromicity observed in the irradiated dsDNA solution and also by a fluorometric analysis of DNA unwinding (FADU) assay. Concurrently, the possibility of NIR-II luminescence bioimaging through biological tissues (bovine tooth and chicken flesh) was demonstrated. The proposed concept paves a way for NIR-II imaging guided antimicrobial phototherapy using lanthanide-doped fluoride nanocrystals.

Simultaneous and efficient removal of fluoride and phosphate in phosphogypsum leachate by acid-modified sulfoaluminate cement.

The high concentration of fluoride and phosphate in phosphogypsum leachate is harmful to the environment and ecosystem. Thus, there is a need to develop feasible materials or technologies to remove both fluoride and phosphate in acidic phosphogypsum leachate. In this study, sulfoaluminate cement (SC) was used to simultaneously remove fluoride and phosphate in wastewater based on its moderate alkalinity and rich content of metal elements (Ca, Al and Fe, etc). The acidized sulfoaluminate cement (ASC) composite was prepared through modifying SC with hydrochloric acid, which can increase the specific surface areas of the raw SC, as well as the activity of the metal elements in SC. Compared with other coagulants, ASC showed excellent removal performance for fluoride and phosphate, such as higher removal efficiency, better effluent quality, and accelerated settling rate. The fluoride and phosphate removal performances of ASC herein were investigated at different dosages, pH values, coexisting substances, and initial concentrations. As a result, ASC exhibited wide pH adaptability and satisfactory selectivity for fluoride and phosphate. The possible removal mechanisms of fluoride and phosphate by ASC included chemisorption, ion exchange, and precipitation. The main end products associated with fluoride were fluorite (CaF2), aluminum fluoride (AlF3), and iron trifluoride (FeF3). The main final products amid phosphate removal, on the other hand, were brushite (CaHPO4·2H2O), aluminophosphate ((H3O)·AlP2O6(OH)2), silicocarnotite (Ca2SiO4·Ca3(PO4)2) and iron phosphate (Fe(H2PO4)3). More importantly, ASC can effectively treat the phosphogypsum leachate at a wide range of concentrations, and the concentrations of phosphate and fluoride in the effluents were lower than 0.5 mg P L-1 and 4 mg L-1, respectively. To sum up, ASC is a competitive candidate to treat wastewater with high fluoride and phosphate content, such as phosphogypsum leachate.

AFM and SEM/EDS characterization of surfaces of fluorine-releasing bulk-fill restorative materials aged in common liquids.

PURPOSE: This study investigated the surface roughness (SR), surface microhardness (SH), and chemical composition of recently developed fluoride-releasing restorative materials aged in common liquids. METHODS: A total of 276 disc-shaped samples with a diameter of 8 mm and a height of 2 mm were prepared by using four restorative materials: alkasite, Activa, Equia Forte, and Zirconomer. Atomic force microscopy (AFM) and the Vickers microhardness test were used to measure SR and SH, respectively. Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM/EDS) was used for elemental analysis of the materials. The prepared samples were divided into 3 subgroups and immersed in coffee, cola, and saliva for 1 week at 37°C and 100% humidity. RESULTS: Cola and coffee significantly increased the SR of all materials except Zirconomer immersed in coffee (P < 0.05). The microhardness of alkasite and Activa significantly decreased in all liquids (P < 0.05) The percentage of fluorine (F) in the materials significantly changed after immersion for some liquids (P < 0.05). CONCLUSION: Aging differentially affected the surface characteristics and elemental mass ratios of the studied materials.

Groundwater defluoridation efficacy of manganese-oxide-coated alumina prepared via two-step heating.

Fluoride concentrations in groundwater can be high in some Brazilian aquifers and therefore these waters should be treated before consumption. This study assessed the properties of Mn-oxide-coated alumina (AM) prepared by two-step heating in water defluoridation. The release of secondary contaminants (e.g. Al3+ and Mn2+) from alumina was also examined, as their removal by vermiculite. The process of Mn-oxide coating changed some properties of the activated alumina (AA), decomposing the crystalline phases and reducing some parameters, e.g. specific surface area (from 295.90 to 94.51 m2 g-1) and pHPZC (from 7.34 to 5.74). These changes increased the efficiency and kinetics of alumina in removing F- from synthetic solutions and groundwater (from 80%/16 h to 100%/1 h). This efficiency was not affected by the presence of other anions in groundwater, such as HCO3- and SO42-. The optimum rate of F- removal occurred at pH 5; however, during the F- removal, Al3+ and Mn2+ ions were released, respectively, from the AA (0.61 mg L-1 Al3+) and from the AM ( 52 mg L-1 Mn2+). Vermiculite used to remove these cations adsorbed about 86% Al3+ and 90% Mn2+. However, only Al3+ concentrations fell below the standard limit for drinking water of <0.5 mg L-1. Therefore, AA has the advantage of not containing Mn, and after 3 h kept F- concentrations in solutions 5 mg L-1F- below the standard limit of 1.5 mg L-1. This study revealed that, depending on the groundwater characteristics, AA may be more efficient and sustainable for defluoridation than coated alumina.

Beyond dissolution: Xerostomia rinses affect composition and structure of biomimetic dental mineral in vitro.

Xerostomia, known as dry mouth, is caused by decreased salivary flow. Treatment with lubricating oral rinses provides temporary relief of dry mouth discomfort; however, it remains unclear how their composition affects mineralized dental tissues. Therefore, the objective of this study was to analyze the effects of common components in xerostomia oral rinses on biomimetic apatite with varying carbonate contents. Carbonated apatite was synthesized and exposed to one of the following solutions for 72 hours at varying pHs: water-based, phosphorus-containing (PBS), mucin-like containing (MLC), or fluoride-containing (FC) solutions. Post-exposure results indicated that apatite mass decreased irrespective of pH and solution composition, while solution buffering was pH dependent. Raman and X-ray diffraction analysis showed that the addition of phosphorus, mucin-like molecules, and fluoride in solution decreases mineral carbonate levels and changed the lattice spacing and crystallinity of bioapatite, indicative of dissolution/recrystallization processes. The mineral recrystallized into a less-carbonated apatite in the PBS and MLC solutions, and into fluorapatite in FC. Tap water did not affect the apatite lattice structure suggesting formation of a labile carbonate surface layer on apatite. These results reveal that solution composition can have varied and complex effects on dental mineral beyond dissolution, which can have long term consequences on mineral solubility and mechanics. Therefore, clinicians should consider these factors when advising treatments for xerostomia patients.

Fluoride concentration in teeth of the roe deer (Capreolus capreolus) and red deer (Cervus elaphus) from areas of Poland industrially uncontaminated with fluoride compounds.

The last biomonitoring study in Poland on intoxication with fluoride compounds of deer was conducted almost two decades ago. Given the fact that fluoride level in air and water is not widely monitored in Poland, it is justified to undertake monitoring of F- levels in people and other long-lived mammals. This paper provides the assessment of the present level of fluoride accumulation in mineralized tissue of large herbivorous mammals. The aim of the present study was to determine fluoride concentration in teeth of deer inhabiting the areas of Poland which are industrially uncontaminated with fluoride compounds, to establish possible correlations between the analysed parameters, and to provide a comparison of the present results with those obtained in other studies. Mean concentration of fluoride in all analysed samples amounted to 231.0 F mg/kg, with the minimum value of 22.0 F mg/kg and the maximum of 935.0 F mg/kg. This results from the development of industry and a widespread use of fluoride-supplemented caries prevention products which contributes to an intense accumulation of these substances in vertebrates, predominantly in mineralized tissue.

Kinetics of ion release from a conventional glass-ionomer cement.

Release kinetics for sodium, silicon, aluminium, calcium and phosphorus from conventional glass-ionomer dental cement has been studied in neutral and acid conditions. Specimens (6 mm height × 4 mm diameter) were made from AquaCem (Dentsply, Konstanz, Germany), 6 per experiment. They were matured (37 °C, 1 h), then placed in 5 cm3 storage solution at 20-22 °C. In the first experiment, deionised water, changed daily for 28 days, was used. In the second, deionised water, changed monthly for 21 months, was used. In the third, lactic acid (20 mmol dm-3, pH: 2.7 ± 0.1), changed monthly for 21 months was used. After storage each solution was analyzed by inductively coupled plasma-optical emission spectroscopy (ICP-OES). Results showed that in neutral conditions, no calcium was released, but in acid, significant amounts were released. The other elements (Na, Al, Si and P) were released in neutral as well as acid conditions, with greater amounts in acid. More frequent changes of water gave greater release. In neutral conditions, release over 21 months followed the equation: [E]c = [E]1t/(t + t½) + ß√t ([E]c is the cumulative release of the element). In acid conditions, this became: [E]c = [E]1t/(t + t½) + αt. Hence release of all elements was shown to occur in two steps, a rapid initial one (half-life: 12-18 h) and a longer second one. In neutral conditions, the longer step involves diffusion; in acid it involves erosion. These patterns influence the material's bioactivity.

ATP Analogues for Structural Investigations: Case Studies of a DnaB Helicase and an ABC Transporter.

Nucleoside triphosphates (NTPs) are used as chemical energy source in a variety of cell systems. Structural snapshots along the NTP hydrolysis reaction coordinate are typically obtained by adding stable, nonhydrolyzable adenosine triphosphate (ATP) -analogues to the proteins, with the goal to arrest a state that mimics as closely as possible a physiologically relevant state, e.g., the pre-hydrolytic, transition and post-hydrolytic states. We here present the lessons learned on two distinct ATPases on the best use and unexpected pitfalls observed for different analogues. The proteins investigated are the bacterial DnaB helicase from Helicobacter pylori and the multidrug ATP binding cassette (ABC) transporter BmrA from Bacillus subtilis, both belonging to the same division of P-loop fold NTPases. We review the magnetic-resonance strategies which can be of use to probe the binding of the ATP-mimics, and present carbon-13, phosphorus-31, and vanadium-51 solid-state nuclear magnetic resonance (NMR) spectra of the proteins or the bound molecules to unravel conformational and dynamic changes upon binding of the ATP-mimics. Electron paramagnetic resonance (EPR), and in particular W-band electron-electron double resonance (ELDOR)-detected NMR, is of complementary use to assess binding of vanadate. We discuss which analogues best mimic the different hydrolysis states for the DnaB helicase and the ABC transporter BmrA. These might be relevant also to structural and functional studies of other NTPases.

Semiquantitative immunochromatographic colorimetric biosensor for the detection of dexamethasone based on up-conversion fluorescent nanoparticles.

A low-cost bifunctional immunochromatographic colorimetric biosensor was developed that can be read visually or by using an optical density scanner. Five test lines (T lines) coated with different antigens were set on a nitrocellulose (NC) membrane to indicate the concentration of analyte. This method was applied for the detection of dexamethasone. The corresponding detection range was 0.1-9 ng mL-1, and the detection limit for dexamethasone in food supplements and cosmetic samples was 2.0 µg kg-1. For visual inspection of the colour the quantitative relative error range between the proposed method and liquid chromatography was -62 to -25%, with a detection time of only 10 min. More accurate assay results were obtained by using an optical density scanner with the relative error range of -31 to 20%. The results indicated that the proposed method has the potential of application for rapid and efficient screening of dexamethasone in cosmetics and food supplements. Graphical abstract.

Unmodified Rose Bengal photosensitizer conjugated with NaYF4:Yb,Er upconverting nanoparticles for efficient photodynamic therapy.

In photodynamic therapy (PDT), photosensitizer (PS) molecules are irradiated by light to generate reactive oxygen species (ROS), the presence of which subsequently leads to cell death. At present, the modality is limited to the treatment of skin diseases because of the low tissue penetration of visible or ultraviolet light required for producing ROS. To increase tissue penetration and extend the therapeutic possibilities of PDT to the treatment of deep-seated cancer, rare-earth doped nanoparticles capable of up-converting infrared to visible light are investigated. These up-converting nanoparticles (UCNPs) are conjugated with PS molecules to efficiently generate ROS. In this work, we employ hexagonal ß-NaYF4:Yb3 + ,Er3 + as UCNPs and Rose Bengal (RB) as PS molecules and demonstrate efficient in vitro PDT using this nanoformulation. Covalent bonding of the RB molecules is accomplished without their functionalization-an approach which is expected to increase the efficiency of ROS generation by 30%. Spectroscopic studies reveal that our approach results in UCNP surface fully covered with RB molecules. The energy transfer from UCNPs to RB is predominantly non-radiative as evidenced by luminescence lifetime measurements. As a result, ROS are generated as efficiently as under visible light illumination. The in vitro PDT is tested on murine breast 4T1 cancer cells incubated with 250 µg ml-1 of the nanoparticles and irradiated with NIR light under power density of 2 W cm-2 for 10 minutes. After 24 hours, the cell viability decreased to 33% demonstrating a very good treatment efficiency. These results are expected to simplify the protocols for preparation of the PDT agents and lead to improved therapeutic effects.

NIR-Driven Water Splitting H2 Production Nanoplatform for H2-Mediated Cascade-Amplifying Synergetic Cancer Therapy.

As a newly emerging treatment strategy for many diseases, hydrogen therapy has attracted a lot of attention because of its excellent biosafety. However, the high diffusivity and low solubility of hydrogen make it difficult to accumulate in local lesions. Herein, we develop a H2 self-generation nanoplatform by in situ water splitting driven by near-infrared (NIR) laser. In this work, core-shell nanoparticles (CSNPs) of NaGdF4:Yb,Tm/g-C3N4/Cu3P (UCC) nanocomposites as core encapsulated with zeolitic imidazolate framework-8 (ZIF-8) modified with folic acid as shell are designed and synthesized. Due to the acid-responsive ZIF-8 shell, enhanced permeability and retention (EPR) effect, and folate receptor-mediated endocytosis, CSNPs are selectively captured by tumor cells. Upon 980 nm laser irradiation, CSNPs exhibit a high production capacity of H2 and active oxygen species (ROS), as well as an appropriate photothermal conversion temperature. Furthermore, rising temperature increases the Fenton reaction rate of Cu(I) with H2O2 and strengthens the curative effect of chemodynamic therapy (CDT). The excess glutathione (GSH) in tumor microenvironment (TME) can deplete positive holes produced in the valence band of g-C3N4 in the g-C3N4/Cu3P Z-scheme heterojunction. GSH also can reduce Cu(II) to Cu(I), ensuring a continuous Fenton reaction. Thus, a NIR-driven H2 production nanoplatform is constructed for H2-mediated cascade-amplifying multimodal synergetic therapy.

NaGdF4:Yb,Er-Ag nanowire hybrid nanocomposite for multifunctional upconversion emission, optical imaging, MRI and CT imaging applications.

The effect of novel silver nanowire encapsulated NaGdF4:Yb,Er hybrid nanocomposite on the upconversion emission and bioimaging properties has been investigated. The upconvension nanomaterials were synthesised by polyol method in the presence of ethylene glycol, PVP and ethylenediamine. The NaGdF4:Yb,Er-Ag hybrid was formed with upconverting NaGdF4:Yb,Er nanoparticles of size ~ 80 nm and silver nanowires of thickness ~ 30 nm. The surface plasmon induced by the silver ion in the NaGdF4:Yb,Er-Ag nanocomposite resulted an intense upconversion green emission at 520 nm and red emission at 660 nm by NIR diode laser excitation at 980 nm wavelength. The UV-Vis-NIR spectral absorption at 440 nm and 980 nm, the intense Raman vibrational modes and the strong upconversion emission results altogether confirm the localised surface plasmon resonance effect of silver ion in the hybrid nanocomposite. MRI study of both NaGdF4:Yb,Er nanoparticle and NaGdF4:Yb,Er-Ag nanocomposite revealed the T1 relaxivities of 22.13 and 10.39 mM-1 s-1, which are larger than the commercial Gd-DOTA contrast agent of 3.08 mM-1 s-1. CT imaging NaGdF4:Yb,Er-Ag and NaGdF4:Yb,Er respectively showed the values of 53.29 HU L/g and 39.51 HU L/g, which are higher than 25.78 HU L/g of the CT contrast agent Iobitridol. The NaGdF4:Yb,Er and NaGdF4:Yb,Er-Ag respectively demonstrated a negative zeta potential of 54 mV and 55 mV, that could be useful for biological application. The in vitro cytotoxicity of the NaGdF4:Yb,Er tested in HeLa and MCF-7 cancer cell line by MTT assay demonstrated a cell viability of 90 and 80 %, respectively. But, the cell viability of NaGdF4:Yb,Er-Ag slightly decreased to 80 and 78%. The confocal microscopy imaging showed that the UCNPs are effectively up-taken inside the nucleolus of the cancer cells, and it might be useful for NIR laser-assisted phototherapy for cancer treatment. Graphical abstract.

Poly(selenoviologen)-Assembled Upconversion Nanoparticles for Low-Power Single-NIR Light-Triggered Synergistic Photodynamic and Photothermal Antibacterial Therapy.

The development of a highly effective photosensitizer (PS) that can be activated with a low-power single light is a pressing issue. Herein, we report a PS for synergistic photodynamic and photothermal therapy constructed through self-assembly of poly(selenoviologen) on the surface of core-shell NaYF4:Yb/Tm@NaYF4 upconversion nanoparticles. The hybrid UCNPs/PSeV PS showed strong ROS generation ability and high photothermal conversion efficiency (∼52.5%) under the mildest reported-to-date irradiation conditions (λ = 980 nm, 150 mW/cm2, 4 min), leading to a high efficiency in killing methicillin-resistant Staphylococcus aureus (MRSA) both in vitro and in vivo. Remarkably, after intravenous injection, the reported PS accumulated preferentially in deep MRSA-infected tissues and achieved an excellent therapeutic index. This PS design realizes a low-power single-NIR light-triggered synergistic phototherapy and provides a simple and versatile strategy to develop safe clinically translatable agents for efficient treatment of deep tissue bacterial inflammations.

Selective Decoating-Induced Activation of Supramolecularly Coated Toxic Nanoparticles for Multiple Applications.

In spite of the rapid emergence of numerous nanoparticles (NPs) for biomedical applications, it is often challenging to precisely control, or effectively tame, the bioactivity/toxicity of NPs, thereby exhibiting limited applications in biomedical areas. Herein, we report the construction of hyaluronic acid (HA)-laminated, otherwise toxic methylviologen (MV), NPs via ternary host-guest complexation among cucurbit[8]uril, trans-azobenzene-conjugated HA, and MV-functionalized polylactic acid NPs (MV-NPs). The high, nonspecific toxicity of MV-NPs was effectively shielded (turned off) by HA lamination, as demonstrated in cells, zebrafish, and mouse models. The supramolecular host-guest interaction-mediated HA coating offered several HA-MV-NP modalities, including hyaluronidase locally and photoirradiation remotely, to precisely remove HA lamination on demand, thereby endowing materials with the capability of selective decoating-induced activation (DIA) for applications as a user-friendly herbicide, a selective antibacterial agent, or an anticancer nanomedicine. This work offers facile supramolecular coating and DIA strategies to effectively tame and precisely control the bioactivity and toxicity of functional nanomaterials for diverse applications.

Construction of a near-infrared responsive upconversion nanoplatform against hypoxic tumors via NO-enhanced photodynamic therapy.

Photodynamic therapy (PDT) has been extensively used to treat cancer and other malignant diseases because it can offer many unique advantages over other medical treatments such as less invasive, fewer side effects, lower cost, etc. Despite great progress, the efficiency of PDT treatment, as an oxygen-dependent therapy, is still limited by the hypoxic microenvironment in the human tumor region. In this work, we have developed a near-infrared (NIR) activated theranostic nanoplatform based on upconversion nanoparticles (UCNPs), which incorporates PDT photosensitizer (curcumin) and NO donor (Roussin's black salt) in order to overcome hypoxia-associated resistance by reducing cellular respiration with NO presence in the PDT treatment. Our results suggest that the photo-released NO upon NIR illumination can greatly decrease the oxygen consumption rate and hence increase singlet oxygen generation, which ultimately leads to an increased number of cancer cell deaths, especially under hypoxic condition. It is believed that the methodology developed in this study enables to relieve the hypoxia-induced resistance in PDT treatment and also holds great potential for overcoming hypoxia challenges in other oxygen-dependent therapies.

Activatable Photodynamic Therapy with Therapeutic Effect Prediction Based on a Self-correction Upconversion Nanoprobe.

Though emerging as a promising therapeutic approach for cancers, the crucial challenge for photodynamic therapy (PDT) is activatable phototoxicity for selective cancer cell destruction with low "off-target" damage and simultaneous therapeutic effect prediction. Here, we design an upconversion nanoprobe for intracellular cathepsin B (CaB)-responsive PDT with in situ self-corrected therapeutic effect prediction. The upconversion nanoprobe is composed of multishelled upconversion nanoparticles (UCNPs) NaYF4:Gd@NaYF4:Er,Yb@NaYF4:Nd,Yb, which covalently modified with an antenna molecule 800CW for UCNPs luminance enhancement under NIR irradiation, photosensitizer Rose Bengal (RB) for PDT, Cy3 for therapeutic effect prediction, and CaB substrate peptide labeled with a QSY7 quencher. The energy of UCNPs emission at 540 nm is transferred to Cy3/RB and eventually quenched by QSY7 via two continuous luminance resonance energy transfer processes from interior UCNPs to its surface-extended QSY7. The intracellular CaB specifically cleaves peptide to release QSY7, which correspondingly activates RB with reactive oxygen species (ROS) generation for PDT and recovers Cy3 luminance for CaB imaging. UCNPs emission at 540 nm remains unchanged during the peptide cleavage process, which is served as an internal standard for Cy3 luminance correction, and the fluorescence intensity ratio of Cy3 over UCNPs (FI583/FI540) is measured for self-corrected therapeutic effect prediction. The proposed self-corrected upconversion nanoprobe implies significant potential in precise tumor therapy.