Narrow-Band Red-Emitting Phosphors with High Color Purity, Trifling Thermal and Concentration Quenching for Hybrid White LEDs and Li3Y3BaSr(MoO4)8:Sm3+, Eu3+-Based Deep-Red LEDs for Plant Growth Applications.

Trivalent europium-based monochromatic red light-emitting phosphors are an essential component to realize high-performance smart lighting devices; however, the concentration and thermal quenching restrict their usage. Here, we report a series of efficient Eu3+-substituted Li3Y3BaSr(MoO4)8 red-emitting phosphors based on a stratified scheelite structure with negligible concentration and thermal quenching. All of the host and phosphor compositions crystallize in monoclinic crystal structure (space group C2/c). All of the phosphor compositions produce narrow-band red emission (FWHM ∼6 nm), which is highly apparent to the human eyes, and lead to exceptional chromatic saturation of the red spectral window. Concurrently, detailed investigations were carried out to comprehend the concentration and thermal quenching mechanism. Absolute quantum yields as high as 88.5% were obtained for Li3Y0.3Eu2.7BaSr(MoO4)8 phosphor with virtuous thermal stability (at 400 K, retaining 87% of its emission intensity). The light-emitting diodes were constructed by coupling Li3BaSrY0.3Eu2.7(MoO4)8 red phosphor with a near-UV LED chip (395 nm) operated at 20 mA forward bias, and the hybrid white LED (an organic yellow dye + red Li3Y3BaSr(MoO4)8:Eu3+ phosphor integrated with an NUV LED chip) showed a low CCT (6645 K), high CRI (83) values, and CIE values of x = 0.303; y = 0.368, which indicated that the synthesized phosphors can be a suitable red component for white LEDs. In addition, we have systematically investigated the Sm3+ and Sm3+, Eu3+ activation in Li3Y3BaSr(MoO4)8 to display the latent use of the system in plant growth applications and establish that the phosphor exhibits orange red emission with an intense deep-red emission (645 nm (4G5/2 → 6H9/2)). The phytochrome (Pr) absorption spectrum well matched the fabricated deep-red LED (by integrating a NUV LED + Li3Y3BaSr(MoO4)8:Sm3+ and Eu3+ phosphor) spectral lines.

Zero-concentration quenching: a novel Eu3+ based red phosphor with non-layered crystal structure for white LEDs and NaSrY(MoO4)3:Sm3+ based deep-red LEDs for plant growth.

Oxide based highly efficient narrow band red emitting phosphors are still a bottleneck in white LED applications. Trivalent europium ion based phosphors could be a better choice, however their weak oscillator strength restricts their use in white light emitting diodes (LEDs). Herein, we report a novel red emitting NaSrEu(MoO4)3 (NSEuM) phosphor with zero concentration quenching (non-layered crystal structure). The phosphors (NaSrY1-xEux(MoO4)3, x = 0.1-1, in increments of 0.1) were synthesized through a traditional solid-state reaction and their phase formations were analyzed by powder X-ray diffraction (PXRD) followed by Rietveld refinement. Under 395 nm excitation, all the phosphors showed sharp emission at 616 nm (full width at half maximum, FWHM ∼4-5 nm) owing to the 5D0→7F2 electric dipole transition of the Eu3+ ion. A concentration dependent photoluminescence (PL) study revealed that there is no concentration quenching of the systems, leading to them having superior emission characteristics over those of commercial red phosphors as well as a reported Eu3+ phosphor with a layered structure. The color purity of the synthesized phosphor was observed to be 96.32% and it shows excellent thermal stability at 423 K, retaining 64.6% of the emission intensity of its initial room temperature. The NSEuM phosphor shows a high absolute quantum yield of 79.7%. Besides this, a red LED (near UV (NUV) LED chip with the NaSrEu(MoO4)3 phosphor) as well as a hybrid white LED (NUV LED chip with an organic yellow dye + red NSEuM phosphor) were fabricated and their optical properties were studied. After the inclusion of the red phosphor in the hybrid white LED, the color rendering index (CRI)/correlated color temperature (CCT) were improved significantly (60/9333 K vs. 79/6004 K, respectively). In addition, to show the potential use of the system in plant growth application, we systematically investigated the Sm3+ activation in NaSrY(MoO4)3 and found that the phosphor shows orange red emission with an intense deep red emission (645 nm (4G5/2→6H9/2)). We fabricated a hybrid red/deep red LED by integrating a NUV LED with a mixed Sm3+ and Eu3+ phosphor and the spectral lines were well matched with the phytochrome (Pr) absorption spectrum. The presently investigated phosphor showed potential in a white LED as well as a deep red/orange-red LED for plant growth.

A CD44-targeted Cu(ii) delivery 2D nanoplatform for sensitized disulfiram chemotherapy to triple-negative breast cancer.

Recent studies have suggested that the anticancer activity of disulfiram (DSF, an FDA-approved alcohol-abuse drug) is Cu-dependent. Low system toxicity and explicit pharmacokinetic characteristics of DSF necessitate safe and effective Cu supplementation in local lesion for further applications. Herein, we presented a new conceptual 'nanosized coordination transport' strategy of Cu(ii) that was realized in porphyrin-based metal-organic frameworks, Sm-TCPP, with strong binding ability to Cu(ii) due to their coordination interactions. Sm-TCPP(Cu) was coated by hyaluronic acid (HA) that termed by Sm-TCPP(Cu)@HA, acting as 'beneficial horse' to target the tumor-localized HA receptor (CD44), thus liberating Cu(ii) ions in cellular overexpressed reductants. The CD44-mediated Cu(ii) accumulation efficiency of Sm-TCPP(Cu)@HA was benchmarked in vitro and vivo against the free TCPP (Cu) via ICP-MS analysis. More importantly, the sensitization effects of Sm-TCPP(Cu)@HA on the anticancer activity of DSF were demonstrated in vivo and in vitro. This study offered a new class of targeted Cu supplements to sensitize DSF for the effective treatment of cancer and established a versatile methodology for constructing a safe and specific delivery of metal ions within living organisms.

Intense green-, red-emitting Tb3+ , Tb3+ /Bi3+ -doped and Sm3+ , Sm3+ /La3+ -doped Ca2 Al2 SiO7 phosphors.

This paper focuses on an optical study of a Tb3+ /Bi3+ -doped and Sm3+ /La3+ - doped Ca2 Al2 SiO7 phosphor synthesized using combustion methods. Here, Ca2 Al2 SiO7 :Sm3+ showed a red emission band under visible light excitation but, when it co-doped with La3+ ions, the emission intensity was further enhanced. Ca2 Al2 SiO7 :Tb3+ shows the characteristic green emission band under near-ultraviolet light excitation wavelengths, co-doping with Bi3+ ions produced enhanced photoluminescence intensity with better colour tunable properties. The phosphor exhibited better phase purity and crystallinity, confirmed by X-ray diffraction. Binding energies of Ca(2p), Al(2p), Si(2p), O(1s) were studied using X-ray photoelectron spectroscopy. The reported phosphor may be a promising visible light excited red phosphor for light-emitting diodes and energy conversion devices.

High-Throughput Synthesis and Characterization of Eu Doped Ba xSr2- xSiO4 Thin Film Phosphors.

High-throughput techniques have been employed for the synthesis and characterization of thin film phosphors of Eu-doped Ba xSr2- xSiO4. Direct synthesis from evaporation of the constituent elements under a flux of atomic oxygen on a sapphire substrate at 850 °C was used to directly produce thin film libraries (415 nm thickness) of the crystalline orthosilicate phase with the desired compositional variation (0.24 > x > 1.86). The orthosilicate phase could be synthesized as a pure, or predominantly pure, phase. Annealing the as synthesized library in a reducing atmosphere resulted in the reduction of the Eu while retaining the orthosilicate phase, and resulted in a materials thin film library where fluorescence excited by blue light (450 nm) was observable by the naked eye. Parallel screening of the fluorescence from the combinatorial libraries of Eu doped Ba xSr2- xSiO4 has been implemented by imaging the fluorescent radiation over the library using a monochrome digital camera using a series of color filters. Informatics tools have been developed to allow the 1931 CIE color coordinates and the relative quantum efficiencies of the materials library to be rapidly assessed and mapped against composition, crystal structure and phase purity. The range of compositions gave values of CIE x between 0.17 and 0.52 and CIE y between 0.48 and 0.69 with relative efficiencies in the range 2.0 × 10-4-7.6 × 10-4. Good agreement was obtained between the thin film phosphors and the fluorescence characteristics of a number of corresponding bulk phosphor powders. The thermal quenching of fluorescence in the thin film libraries was also measured in the temperature range 25-130 °C: The phase purity of the thin film was found to significantly influence both the relative quantum efficiency and the thermal quenching of the fluorescence.

APPLICATION OF DROPLET DETECTORS TO ALPHA RADIATION DETECTION.

Superheated droplet detectors (SDDs) are traditionally employed in the detection of neutrons. In this work the focus is on the detection of alpha particles using C2ClF5 as the target liquid. The alpha-droplet interaction is examined via computational studies, and a geometric model developed to describe the expected detector response. Experiments with alpha-emitting uranium- and samarium-doped SDDs at temperatures of 5-12°C confirm that the event rate is related to the size of the droplets, and are in model agreement for temperatures below 8°C; above this temperature, the acoustic sensitivity is reduced by signal attenuation as a result of the increasing bubble population, for which the addition of an attenuation coefficient restores the agreement with experiment. The results suggest the viability of a SDD-based alpha spectrometer using mono-sized droplets.

Cyclization into Hydrindanes Using Samarium Diiodide: Stereochemical Features Depending on the Protecting Group.

Monocyclic compounds bearing ketone and enone moieties in the same molecule can be cyclized to bicyclic compounds initiated by samarium diiodide. The stereochemistry of the products depended on the reaction conditions and also the protecting group of the hydroxy group existed in the molecule. A cyclization mechanism-is discussed.

Synthesis of a key intermediate, 10-acetyl-7-(t-butyldiphenylsilyloxymethyl)-4-methylbicyclo[5.3.0]dec-4-en-1-ol, in the synthesis of pseudolaric acid A.

10-Acetyl-7-(t-butyldiphenylsilyloxymethyl)-4-methylbicyclo[5.3.0]dec-4-en-1-ol was synthesized by aldol cyclization to a five-membered ring, epoxidation, samarium diiodide-induced ring opening, and the RCM reaction to the seven-membered carbocycle. This method has succeeded in constructing the desired stereochemistry in the synthesis of pseudolaric acid A.

Enhanced photoactivity of Sm, N, P-tridoped anatase-TiO2 nano-photocatalyst for 4-chlorophenol degradation under sunlight irradiation.

A novel high-performance Sm, N, P-tridoped anatase-TiO2 nano-photocatalyst (SNPTO) was successfully prepared by a modified sol-solvothermal process. The physicochemical properties of as-prepared samples were characterized by X-ray diffraction, transmission electron microscopy, N2 adsorption-desorption isotherm, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, UV-vis absorbance spectroscopy, photoluminescence spectroscopy, and zeta potential measurements. The results showed that, among as-prepared undoped, single-doped, and codoped samples, SNPTO presented the highest photoactivity for degrading 4-chlorophenol (4-CP) under simulated sunlight irradiation with the apparent rate constant of 2.83×10(-2)min(-1), which was 3.98 times more than that of commercial P25 TiO2 (kapp=7.11×10(-3)min(-1)). The TOC removal rate for 4-CP solution (20 mg L(-1)) in the presence of SNPTO (0.4 g L(-1)) reached 87.13% after simulated sunlight irradiation for 120 min, indicating that 4-CP could be mineralized efficiently. Experiments concerning radical scavengers indicated that OH in the solution was the main reactive species. The enhanced photoactivity of SNPTO was attributed to a synergistic effect of the more efficient inhibition of the recombination of photogenerated electrons and holes, the increase in the visible light absorption ability, surface hydroxyl and specific surface area, as well as the improvement of the surface textural properties. SNPTO exhibited good photochemical stability and could be reused for 5 times with less than 1.6% decrease in the 4-CP removal efficiency.

Measurement of cross sections for the 147Sm(n, alpha)144Nd reaction at 5.0 and 6.0 MeV.

Cross sections of the (147)Sm(n, alpha)(144)Nd reaction were measured at En=5.0 and 6.0MeV. A twin gridded ionization chamber was used as a charged particle detector and two large area (147)Sm(2)O(3) samples placed back to back were employed. Experiments were performed at the 4.5MV Van de Graaff accelerator of Peking University. Neutrons were produced through the D(d, n)(3)He reaction with a deuterium gas target. Absolute neutron flux was determined by a small (238)U fission chamber. Present cross-section data are compared with existing results of evaluations and measurements.

Fluorimetric determinations of nucleic acids using iron, osmium and samarium complexes of 4,7-diphenyl-1,10-phenanthroline.

New sensitive, reliable and reproducible fluorimetric methods for determining microgram amounts of nucleic acids based on their reactions with Fe(II), Os(III) or Sm(III) complexes of 4,7-diphenyl-1,10-phenanthroline are proposed. Two complementary single stranded synthetic DNA sequences based on calf thymus as well as their hybridized double stranded were used. Nucleic acids were found to react instantaneously at room temperature in Tris-Cl buffer pH 7, with the investigated complexes resulting in decreasing their fluorescence emission. Two fluorescence peaks around 388 and 567 nm were obtained for the three complexes using excitation lambda(max) of 280 nm and were used for this investigation. Linear calibration graphs in the range 1-6 microg/ml were obtained. Detection limits of 0.35-0.98 microg/ml were obtained. Using the calibration graphs for the synthetic dsDNA, relative standard deviations of 2.0-5.0% were obtained for analyzing DNA in the extraction products from calf thymus and human blood. Corresponding Recovery% of 80-114 were obtained. Student's t-values at 95% confidence level showed insignificant difference between the real and measured values. Results obtained by these methods were compared with the ethidium bromide method using the F-test and satisfactory results were obtained. The association constants and number of binding sites of synthetic ssDNA and dsDNA with the three complexes were estimated using Rosenthanl graphic method. The interaction mechanism was discussed and an intercalation mechanism was suggested for the binding reaction between nucleic acids and the three complexes.

Orthodontic magnets. A study of force and field pattern, biocompatibility and clinical effects.

Magnetic forces have been incorporated into orthodontic mechanics during recent years. However, the biocompatibility of magnet alloys and the possible risk of harmful or unusual reactions in tissues exposed to static magnetic fields have been characterized as inconsistent and often contradictory. It has also been questioned whether magnetic forces have significant advantages over traditional mechanics. The present series of studies aimed to analyse the force and field properties, the biocompatibility and the clinical effects of rare earth magnets as well as to compare the efficiency of tooth movement between magnets and another force system. Samarium-cobalt magnets for molar distalization were tested in experimental models for force and field properties. The cytotoxicity of different magnet alloys (rare earth types) as well as of clinically used and recycled magnets was assessed by two in vitro methods, the millipore filter method and an extraction method. The effect of static magnetic fields on human gingival tissue and dental pulp was examined histologically for alterations in cell pattern and cell morphology. The effects of using repelling samarium-cobalt magnets for simultaneous distalization of maxillary first and second molars were analysed in individuals with Class II malocclusion. The efficiency of molar distalization was also intra-individually compared between repelling magnets and superelastic NiTi-coils in individuals with Class II malocclusion and deep bite. The magnet forces decreased approximately with the reciprocal square of the separation distance between the magnets. No fatigue of force over time could be seen. The static magnetic fields were weak and had a limited extent and the flux density dropped exponentially in all directions with increased distance from the magnets, implying a small exposure area when the magnets are used clinically. Rare earth magnets showed good biocompatibility, particularly coated magnets. However, uncoated samarium-cobalt magnets showed significant cytotoxicity. It was also found that stainless-steel-coated samarium-cobalt magnets could be recycled with maintained good biocompatibility. After exposure to static magnetic fields, normal clinical and histological conditions in the human gingival tissue and normal histological features in the human dental pulp were found. Repelling magnets were effective in producing maxillary molar distalization but some side effects like anchorage loss and molar tipping were found. The superelastic coils were shown to be even more efficient than the repelling magnets for maxillary molar distalization in individuals with Class II malocclusion and deep bite.

Chemistry and biological behavior of samarium-153 and rhenium-186-labeled hydroxyapatite particles: potential radiopharmaceuticals for radiation synovectomy.

Hydroxyapatite (HA), a natural constituent of bone, was studied as a particulate carrier for beta-emitting radionuclides in radiation synovectomy. Particles were radiolabeled with 153Sm or 186Re and their in vivo safety was investigated following intra-articular injection into knees of normal rabbits and rabbits with antigen-induced arthritis (AIA). Radiolabeling efficiency was greater than 95%; in vitro studies showed minimal (< or = 1%) loss of activity from particles over a 6-day period with 153Sm-labeled HA and about 5% loss of activity over a 5-day period with 186Re-labeled HA. The total cumulative extra-articular leakage of 153Sm over 6 days was 0.28% in normal rabbits and 0.09% in AIA rabbits. Leakage of 186Re from the joint was 3.05% over a 4-day period with 80% of extra-articular activity found in the urine. Histopathological evaluation of treated knees showed that HA particles are distributed throughout the synovium, embedded in the synovial fat pad. The ease and efficiency with which this HA carrier is labeled, coupled with observed extremely low leakage rates from the joint, make radiolabeled HA particles an attractive candidate as a radiation synovectomy agent for evaluation in rheumatoid arthritis patients.