One-Dimensional Hybrid Copper(I) Iodide Single Crystal with Renewable Scintillation Properties.

Low-dimensional hybrid copper(I) halides attract considerable attention in the field of light emissions. In this work, we obtained the centimeter-sized single crystal of 1,3-propanediamine copper(I) iodide (PDACuI3) with a solvent evaporation method. The single crystal X-ray diffraction of PDACuI3 reveals that the [CuI4] tetrahedra form the corner-connected chains separated by PDAs, forming a one-dimensional structure with an orthorhombic space group of Pbca. The band gap is determined to be 4.03 eV, and the room temperature photoluminescence (PL) quantum yield is determined to be 26.5%. The thermal quenching and negative thermal quenching of emission are observed via temperature-dependent PL spectra, and our study shows that the intermediate nonradiative state below the self-trapped exciton state may get involved in these temperature-dependent behaviors. The X-ray scintillation performance of PDACuI3 single crystals is also evaluated, and the relative light output renewed to 94.3% of the fresh one after a low-temperature annealing. On the basis of our results, PDACuI3 single crystals provide nontoxicity and renewable scintillation performance, thus showing potential application in the area of low-cost radiation detectors.

High-stability double perovskite scintillator for flexible X-ray imaging.

Metal halide perovskites, as a new class of attractive and potential scintillators, are highly promising in X-ray imaging. However, their application is limited by the sensitivity to moisture and irradiation. To address this issue, we reported a 2D layered double perovskite material Cs4Cd1-xMnxBi2Cl12 that exhibits high stability both under ambient condition and under X-ray irradiation. Cs4Cd1-xMnxBi2Cl12 demonstrates superior scintillation performance, including excellent X-ray response linearity and a high light yield (∼34,450 photons/MeV). More importantly, the X-ray excited emission intensity maintains 92% and 94% of its original value after stored at ambient condition for over two years and after X-ray irradiation with a total dose of 11.4 Gy, respectively. By mixing with PDMS (polydimethylsiloxane), we have successfully produced a high-quality flexible film that can be bent freely while maintaining its excellent scintillation properties. The scintillating screen exhibits outstanding imaging ability with a spatial resolution of up to 16.7 line pairs per millimeter (lp/mm), also, the superiority of this scintillation screen in flexible X-ray imaging is demonstrated. These results indicate the huge potential of this high-stability double perovskite scintillator in X-ray imaging.

Temperature-Dependent Luminescence and Anisotropic Optical Properties of Centimeter-Sized One-Dimensional Perovskite Trimethylammonium Lead Iodide Single Crystals.

Low-dimensional hybrid halide perovskite materials with self-trapped exciton (STE) emissions and anisotropic properties are highly attractive for their great potential in many applications. However, to date, reports on large one-dimensional (1D) perovskite single crystals have been limited. Here, centimeter-sized 1D single crystals of trimethylammonium lead iodide (TMAPbI3) with typical STE emission are synthesized by an antisolvent vapor-assisted crystallization method. Thermal quenching and antiquenching with a high relative sensitivity of photoluminescence (PL) are observed and studied via temperature-dependent photoluminescence spectroscopy. Further analysis indicates that the temperature-dependent PL behaviors are influenced by the self-trapping of the free exciton and the migrations between self-trapped excitons and intermediate nonradiative states. The TMAPbI3 single crystal also exhibits a linearly polarized emission and a large birefringence that is higher than those of commercial birefringent crystals. This 1D perovskite with high structural anisotropy has promise for applications in versatile optical- and luminescence-related fields.

A polymer controlled nucleation route towards the generalized growth of organic-inorganic perovskite single crystals.

Recently, there are significant progresses in the growth of organic-inorganic lead halide perovskite single crystals, however, due to their susceptible nucleation and growth mechanisms and solvent requirements, the efficient and generalized growth for these single crystals is still challenging. Here we report the work towards this target with a polymer-controlled nucleation process for the highly efficient growth of large-size high-quality simple ternary, mixed-cations and mixed-halide perovskite single crystals. Among them, the carrier lifetime of FAPbBr3 single crystals is largely improved to 10199 ns. Mixed MA/FAPbBr3 single crystals are synthesized. The crucial point in this process is suggested to be an appropriate coordinative interaction between polymer oxygen groups and Pb2+, greatly decreasing the nuclei concentrations by as much as 4 orders of magnitudes. This polymer-controlled route would help optimizing the solution-based OIHPs crystal growth and promoting applications of perovskite single crystals.

Highly luminescent self-organized sub-2-nm EuOF nanowires.

Monodisperse sub-2-nm EuOF nanowires were obtained by manipulating the fluorophilicity between crystalline seeds and capping surfactant molecules during the thermolysis of Eu(CF(3)COO)(3) in oleic acid (OA) and oleylamine (OM). The uniform EuOF nanowires can self-organize on substrates to form parallel aligned superstructures and display strong Eu(3+)red emissions with high quantum yields of 65% under the UV light excitations due to the presence of dense surface Eu(3+) sites in the ultrathin nanowires as well as the passivation of the surface defects by the capping ligands.

A Facile One-Step Synthesis of Cuprous Oxide/Silver Nanocomposites as Efficient Electrode-Modifying Materials for Nonenzyme Hydrogen Peroxide Sensor.

Cuprous oxide/silver (Cu2O/Ag) nanocomposites were prepared via a facile one-step method and used to construct an electrochemical sensor for hydrogen peroxide (H2O2) detection. In this method, AgNO3 and Cu(NO3)2 were reduced to Cu2O/Ag nanocomposites by glucose in the presence of hexadecyl trimethyl ammonium bromide (CTAB) at a low temperature. The optimum condition was the molar ratio of silver nitrate and copper nitrate of 1:10, the temperature of 50 °C. Under this condition, Cu2O/Ag nanocomposites were obtained with uniformly distributed and tightly combined Cu2O and Ag nanoparticles. The size of Cu2O particles was less than 100 nm and that of Ag particles was less than 20 nm. Electrochemical experiments indicate that the Cu2O/Ag nanocomposites-based sensor possesses an excellent performance toward H2O2, showing a linear range of 0.2 to 4000 µM, a high sensitivity of 87.0 µA mM-1 cm-2, and a low detection limit of 0.2 µM. The anti-interference capability experiments indicate this sensor has good selectivity toward H2O2. Additionally, the H2O2 recovery tests of the sensor in diluted milk solution signify its potential application in routine H2O2 analysis.

Large-scale synthesis of single-crystalline iron oxide magnetic nanorings.

We present an innovative approach to the production of single-crystal iron oxide nanorings employing a solution-based route. Single-crystal hematite (alpha-Fe2O3) nanorings were synthesized using a double anion-assisted hydrothermal method (involving phosphate and sulfate ions), which can be divided into two stages: (1) formation of capsule-shaped alpha-Fe2O3 nanoparticles and (2) preferential dissolution along the long dimension of the elongated nanoparticles (the c axis of alpha-Fe2O3) to form nanorings. The shape of the nanorings is mainly regulated by the adsorption of phosphate ions on faces parallel to c axis of alpha-Fe2O3 during the nanocrystal growth, and the hollow structure is given by the preferential dissolution of the alpha-Fe2O3 along the c axis due to the strong coordination of the sulfate ions. By varying the ratios of phosphate and sulfate ions to ferric ions, we were able to control the size, morphology, and surface architecture to produce a variety of three-dimensional hollow nanostructures. These can then be converted to magnetite (Fe3O4) and maghemite (gamma-Fe2O3) by a reduction or reduction-oxidation process while preserving the same morphology. The structures and magnetic properties of these single-crystal alpha-Fe2O3, Fe3O4, and gamma-Fe2O3 nanorings were characterized by various analytical techniques. Employing off-axis electron holography, we observed the classical single-vortex magnetic state in the thin magnetite nanorings, while the thicker rings displayed an intriguing three-dimensional magnetic configuration. This work provides an easily scaled-up method for preparing tailor-made iron oxide nanorings that could meet the demands of a variety of applications ranging from medicine to magnetoelectronics.

Supramolecular engineering of a 2D Kagomé lattice: synthesis, structures, and magnetic properties.

Two 2D Mn (II) complexes, [Mn3(TzDC)2(phen)3] x 2 H2O (1; H3TzDC = 1,2,3-triazole-4,5-dicarboxylic acid, phen = 1,10-phenanthroline) and [Mn3(TzDC)2(bipy)3] x 4 H2O (2; bipy = 2,2'-bipyridine), were synthesized by hydrothermal reactions and characterized magnetically, and complex 1 was the first example of the chiral complex with a Kagomé lattice connectivity obtained through spontaneous resolution.

Morphometric measurement of the cervical spine for minimally invasive pedicle screw fixation using reverse engineering and three-dimensional reconstruction.

BACKGROUND: Percutaneous cervical pedicle screw fixation has been proven to be an effective method of cervical screw instrumentation, which has the advantages of less invasiveness and low blood loss. Emerging evidence has indicated that the cervical spinous process plays an important role in percutaneous spine surgery. However, there is a limited amount of information on the fundamental research of pedicle and its associated imaging parameter measurement. The purpose of this study was to measure the anatomic data of the pedicle screw channel (PSC) using reverse engineering and three-dimensional reconstruction, and also to discuss the three-dimensional relationship between the cervical spinous process and the pedicle screw channel. METHODS: Twenty adult subjects (10 males, 10 females, age range 19-46 years) were studied using the method of three-dimensional CT reconstruction and reverse engineering. The centrum was divided into 10 equal parts from front to back. The bisectors were defined as borderline depths of the centrum, from front to back, 100%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10%, 0% of borderline depths were presented. Then, a 3D coordinate system was constructed to measure all the data, including the radius of the inscribed circle, the length of the PSC, the insertion angle, the distances from entry point to cervical spinous process and skin depth. All the indexes were measured from 70% to 90% borderline depth. RESULTS: The radius of the inscribed circles from C3 to C7 at 90% borderline depth were 2.94 ± 0.55 mm, 3.04 ± 0.40 mm, 3.15 ± 0.36 mm, 3.28 ± 0.47 mm, 3.89 ± 0.54 mm, respectively. The lengths of the PSC were between 25 and 32 mm. The insertion angles for 70% to 90% borderline depth were 28.33°, 34.28°, 37.92°, respectively. The relationship between the PSC and spinous process was measured as the distance from the entry point to the end of the spinous process, which were, respectively, 26.91 mm, 28.18 mm, 30.03 mm, 35.67 mm, 41.99 mm from C3 to C7 .The distance from the skin to the entry point of C3-7 increased gradually. CONCLUSIONS: The measurements of this study could provide detailed information for percutaneous cervical screw fixation. The data of the relationship between the cervical spinous process and the pedicle screw channel present valuable technical information for the design, optimization and clinical application of the aiming device for percutaneous cervical pedicle screw fixation. Copyright © 2016 John Wiley & Sons, Ltd.

Enhancing capacitance behaviour of CoOOH nanostructures using transition metal dopants by ambient oxidation.

Cobalt hydrate and doped binary Co0.9M0.1OOH (M = Ni, Mn, Fe) nanorings of 100-300 nm were fabricated in solution through a facile ambient oxidation method. A transformation from Co0.9Ni0.1(OH)2 nanodiscs to hollow Co0.9Ni0.1OOH nanorings was observed with prolonged reaction time. Core-shell nanodiscs have elemental segregation with a Co(OH)2 core and Ni(OH)2 shell. Co0.9Ni0.1OOH nanorings displayed a higher electrochemical capacitance than Mn and Fe doped nanorings materials or materials with disc-like geometries.

Phase evolution, texture behavior, and surface chemistry of hydrothermally derived scandium (hydrous) oxide nanostructures.

Nanostructured scandium hydrous oxides were hydrothermally synthesized at 180 degrees C for 18 h, using NaOH, NH(4)OH, and KOH as the bases. They were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption, thermogravimetry and differential thermal analysis (TG-DTA), infrared and Raman spectroscopy, and pyridine adsorption. XRD and TEM measurements showed that the nature and concentration of the bases played key roles in determining the phasic composition, texture behavior (shape and size), and surface chemistry of the hydrothermal products. In addition, the shape evolution of the crystalline products seemed to be closely connected with their crystal structures. As the basicity value was raised from pH 10 to 5 mol L(-1) NaOH (or KOH), alpha-ScOOH nanorods, alpha-ScOOH nanosized hexagonal-like plates, and cubic Sc(OH)3 cubes/cuboids in micrometer size were produced in turn; while within pH 10-12 using NH4OH, gamma-ScOOH nanosized lozenge-like plates were mainly obtained. According to XRD, TEM, and TG-DTA results, all the as-prepared nanostructured ScOOH and micrometric Sc(OH)3 could be converted to cubic Sc2O3 with sustained crystalline shape via calcination at 500 degrees C. Pyridine adsorption revealed the existence of Lewis acid sites on the surfaces of the nanostructured alpha-ScOOH samples and some of their Sc2O3 counterparts calcined at 700 degrees C. The alpha-ScOOH nanorod sample displayed the strongest Lewis acidity among all the samples tested, due to its highest surface area as determined by N2 adsorption. Finally, an olation-oxolation process based on a dissolution/recrystallization mechanism accounts for the formation of various ScOOH polymorphs and Sc(OH)3 with different shapes.

Luminescence resonance energy transfer sensors based on the assemblies of oppositely charged lanthanide/gold nanoparticles in aqueous solution.

This work demonstrates luminescence resonance energy transfer (LRET) sensors based on lanthanide-doped nanoparticles as donors (D) and gold nanoparticles as acceptors (A), combined through electrostatic interactions between the oppositely charged nanoparticles. Negatively charged lanthanide-doped nanoparticles, YVO(4):Eu and LaPO(4):Ce,Tb, with high luminescence quantum yield and good water-solubility, are synthesized through a polymer-assisted hydrothermal method. Positively charged polyhedral and spherical gold nanoparticles exhibit surface plasmon resonance (SPR) bands centered at 623 and 535 nm, respectively. These bands overlap well with the emission of the Eu(3+) and Tb(3+) ions within the lanthanide nanoparticles. Herein, the gold nanoparticles are synthesized through a seed-mediated cetyltrimethylammonium bromide (CTAB)-assisted method. The assemblies of the oppositely charged donors and acceptors are developed into LRET-based sensors exhibiting a donor quenching efficiency close to 100 %.

Single-crystalline and near-monodispersed NaMF3 (M = Mn, Co, Ni, Mg) and LiMAlF6 (M = Ca, Sr) nanocrystals from cothermolysis of multiple trifluoroacetates in solution.

We report the synthesis of single-crystalline and near-monodispersed NaMF3 (M = Mn, Co, Ni, Mg), LiMAlF6 (M = Ca, Sr), and NaMgF3:Yb,Er nanocrystals (quasisquare nanoplates, nanorods, and nanopolygons) by the cothermolysis of multiple trifluoroacetates in hot combined organic solvents (oleic acid, oleylamine, and 1-octadecene). The nanocrystals were characterized by XRD, TEM, superconductive quantum interference device (SQUID), and upconversion luminescence spectroscopy. By regulating the polarity of the dispersant, the NaMF3 (M = Mn, Co, Ni) nanoplates were partially aligned to form nanoarrays on copper TEM grids. The sizes of the NaMF3 nanocrystals were easily tuned by the use of proper synthetic conditions such as reaction temperature and time and solvent composition. On the basis of a series of experiments in which the reaction conditions were varied, together with GC-MS and FTIR analysis, the reaction pathways for the formation of these nanocrystals from trifluoroacetate precursors were proposed. The magnetic measurements showed that the differently sized NaMnF3 square plates displayed interesting weak ferromagnetic behavior on the nanometer scale. The strong red upconversion luminescence emitted from the NaMgF3:Yb,Er nanorods under 980-nm near-IR laser excitation suggests that NaMgF3 may be a good candidate host material for red upconversion luminescence.

From trifluoroacetate complex precursors to monodisperse rare-earth fluoride and oxyfluoride nanocrystals with diverse shapes through controlled fluorination in solution phase.

We report the first systematic synthesis of monodisperse rare-earth (RE=La to Lu, Y) fluoride and oxyfluoride nanocrystals with diverse shapes (trigonal REF3 triangular, truncated-triangular, hexagonal, and polygonal nanoplates; orthorhombic REF3 quadrilateral and zigzag-shaped nanoplates; cubic REOF nanopolyhedra and nanorods) from single-source precursors (SSP) of [RE(CF(3)COO)(3)] through controlled fluorination in oleic acid (OA)/oleylamine (OM)/1-octadecene (ODE). To selectively obtain REF3 or REOF nanocrystals, the fluorination of the RE-O bond to the RE-F bond at the nucleation stage was controlled by finely tuning the ratio of OA/ODE or OA/OM, and the reaction temperature. For phase-pure REF3 or REOF naocrystals, their shape-selective syntheses could be realized by further modifying the reaction conditions. The two-dimensional growth of the REF3 nanoplates and the one-dimensional growth of the REOF nanorods were likely due to the selective adsorption of the capping ligands on specific crystal planes of the nanocrystals. Those well-shaped nanocrystals with diverse geometric symmetries (such as D(3h), D(6h), C(2h), O(h), and D(nh)) displayed a remarkable capability to form self-assembled superlattices. By manipulating the solvent-substrate combination, the plate-shaped REF3 nanocrystals could form highly ordered nanoarrays by means of either the face-to-face formation or the edge-to-edge formation. By using this SSP strategy, we also obtained high-quality LaF3:Eu and LaF3:Eu/LaF3 triangular nanoplates that showed photoluminescent red emissions of Eu3+ ions sensitive to the surface effect.

High-quality sodium rare-earth fluoride nanocrystals: controlled synthesis and optical properties.

We report a general synthesis of high-quality cubic (alpha-phase) and hexagonal (beta-phase) NaREF4 (RE: Pr to Lu, Y) nanocrystals (nanopolyhedra, nanorods, nanoplates, and nanospheres) and NaYF(4):Yb,Er/Tm nanocrystals (nanopolyhedra and nanoplates) via the co-thermolysis of Na(CF3COO) and RE(CF3COO)3 in oleic acid/oleylamine/1-octadecene. By tuning the ratio of Na/RE, solvent composition, reaction temperature and time, we can manipulate phase, shape, and size of the nanocrystals. On the basis of its alpha --> beta phase transition behavior, along the rare-earth series, NaREF4 can be divided into three groups (I: Pr and Nd; II: Sm to Tb; III: Dy to Lu, Y). The whole controlled-synthesis mechanism can be explained from the point of view of free energy. Photoluminescent measurements indicate that the value of I610/I590 and the overall emission intensity of the NaEuF4 nanocrystals are highly correlative with the symmetries of the Eu3+ ions in both the lattice and the surface.

Hierarchical assembly of SnO2 nanorod arrays on alpha-Fe2O3 nanotubes: a case of interfacial lattice compatibility.

SnO2 nanorod arrays were hierarchically assembled onto the surface of alpha-Fe2O3 nanotubes via a facile solution method. Determined by the hexagonal geometrical nature of the alpha-Fe2O3 nanotubes, the heterostructures were of 6-fold symmetry. HRTEM characterizations demonstrated that the lattice mismatch at the interface was an important factor in determining the growth direction of the secondary nanorod arrays.