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We present a comprehensive series of magnetic and neutron scattering measurements of the sawtooth chain compound, CsCo2(MoO4)2(OH). The magnetic properties of CsCo2(MoO4)2(OH) can be easily manipulated by applied magnetic fields.

Radioluminescent multi-doped yttrium pyrosilicate (YPS) nanoparticles were synthesized using a high temperature multi-composite reactor. The luminescent activators explored were cerium, terbium, and europium.

A series of multi-doped yttrium pyrosilicate (YPS) nanoparticles were synthesized using a high temperature multi-composite reactor, and used to explore the radioluminescent properties that have potential for biological applications. The luminescent activators explored in this work were cerium, terbium, and europium. A series of mono-doped YPS nanoparticles were synthesized that have optical and X-ray luminescent properties that span the entire visible spectrum. Energy transfer experiments were investiagted to increase the photo- and X-ray luminescence of terbium and europium. Cerium was used as a sensitizer for terbium where X-ray luminescence was enhanced. Similar results were also obtained using cerium as a sensitizer and terbium as an energy bridge for europium. By leveraging different energy transfer mechanisms X-ray luminescence can be enhanced for YPS nanoparticles.

Hexaferrites have a wide range of technological applications as well as a rich and complicated structural chemistry, with iron oxide layers inducing highly anisotropic ferrimagnetism that remains i...

X-ray excited optical luminescence from nanophosphors can be used to selectively generate light in tissue for imaging and stimulating light-responsive materials and cells. Herein, we synthesized X-ray scintillating NaGdF4:Eu and Tb nanophosphors via co-precipitate and hydrothermal methods, encapsulated with silica, functionalized with biotin, and characterized by X-ray excited optical luminescence spectroscopy and imaging. The nanophosphors synthesized by co-precipitate method were ∼90 and ∼106 nm in diameter, respectively, with hydrothermally synthesized particles showing the highest luminescence intensity. More importantly, we investigated the effect of thermal annealing/calcination on the X-ray excited luminescence spectra and intensity. At above 1000 °C, the luminescence intensity increased, but particles fused together. Coating with a 15 nm thick silica shell prevented particle fusion and enabled silane-based chemical functionalization, although luminescence decreased largely due to the increased mass of non-luminescent material. We observed an increase in luminesce intensity with temperature until at 400 °C. At above 600 °C, NaGdF4:Eu@SiO2 converts to NaGd9Si6O26:Eu, an X-ray scintillator brighter than annealed NPs at 400 °C and dimmer than NPs synthesized using the hydrothermal method. The particles generate light through tissue and can be selectively excited using a focused X-ray source for imaging and light generation applications. The particles also act as MRI contrast agents for multi-modal localization.

X-rays offer low tissue attenuation with high penetration depth when used in medical applications and when coupled with radioluminescent nanoparticles, offer novel theranostic opportunities. In this role, the ideal scintillator requires a high degree of crystallinity for an application relevant radioluminescence, yet a key challenge is the irreversible aggregation of the particles at most crystallization temperatures. In this communication, a high temperature multi-composite reactor (HTMcR) process was successfully developed to recrystallize monodisperse scintillating particulates by employing a core-multishell architecture. The core–shell morphology of the particles consisted of a silica core over-coated with a rare earth (Re = Y 3 + , Lu 3 + , Ce3+) oxide shell. This core–shell assembly was then encapsulated within a poly(divinylbenzene) shell which was converted to glassy carbon during the annealing & crystallization of the silica/rare earth oxide core–shell particle. This glassy carbon acted as a delamination layer and prevented the irreversible aggregation of the particles during the high temperature crystallization step. A subsequent low temperature annealing step in an air environment removed the glassy carbon and resulted in radioluminescent nanoparticles. Two monodisperse nanoparticle systems were synthesized using the HTMcR process including cerium doped Y2Si2O7 and Lu2Si2O7 with radioluminescence peaks at 427 and 399 nm, respectively. These particles may be employed as an in vivo light source for a noninvasive X-ray excited optogenetics.

The structures of seven compounds based on guanidinium cations, isolated sulfate anions, and additional organic cations and solvent molecules are reported. All seven compounds, (C(NH2)3)2(SO4) (1), (C(NH2)3)3(C5H6N)(SO4)2 (2), (C(NH2)3)3(C5H6N)(SO4)2·H2O (3), (C(NH2)3)3(C5H6N)(SO4)2·CH3OH (4), (C(NH2)3)11(C5H6N)(SO4)6·2.5C2H5OH (5), (C(NH2)3)3(C6H16N)(SO4)2 (6), and (C(NH2)3)2(C20H26N2O2)(SO4)2 (7) crystallize without a center of symmetry, and are built of related motifs of six-membered rings via hydrogen bonding of three guanidinium cations and three sulfate anions. These six-membered rings form extended sheets and frameworks through additional hydrogen bonding interactions. The presence of additional cations and solvent molecules in varying ratios add structural diversity by modifying the guanidinium sulfate frameworks, but retaining the acentricity of the structures. The study reveals a remarkable tendency for these guanidinium sulfate frameworks to crystallize without a center of symmetry, and furthermore, in polar or chiral space groups. This provides a potential pathway for the use of hydrogen bonding interactions to design structures having interesting physical or nonlinear optical properties.

An examination of manganese silicates and germanates revealed unusual structural motifs and extremely different chemistries, with identical hydrothermal reactions forming K2Mn2Si3O9 versus K11Mn21Ge32O86(OH)9(H2O). The germanate is exceptional in both its c-axis length (exceeding 76 A) and unit cell volume (nearly 18000 A3), the largest known polygermanate structure to our knowledge.

Two new alkali vanadate carbonates with divalent transition metals have been synthesized as large single crystals via a high-temperature (600 °C) hydrothermal technique. Compound I, Rb2Mn3(VO4)2CO3, crystallizes in the trigonal crystal system in the space group P1c, and compound II, K2Co3(VO4)2CO3, crystallizes in the hexagonal space group P63/m. Both structures contain honeycomb layers and triangular lattices made from edge-sharing MO6 octahedra and MO5 trigonal bipyramids, respectively. The honeycomb and triangular layers are connected along the c-axis through tetrahedral [VO4] groups. The MO5 units are connected with each other by carbonate groups in the ab-plane by forming a triangular magnetic lattice. The difference in space groups between I and II was also investigated with Density Functional Theory (DFT) calculations. Single crystal magnetic characterization of I indicates three magnetic transitions at 77 K, 2.3 K, and 1.5 K. The corresponding magnetic structures for each magnetic transition of I were determined using single crystal neutron diffraction. At 77 K the compound orders in the MnO6-honeycomb layer in a Neel-type antiferromagnetic orientation while the MnO5 triangular lattice ordered below 2.3 K in a colinear ‘up–up–down’ fashion, followed by a planar ‘Y’ type magnetic structure. K2Co3(VO4)2CO3 (II) exhibits a canted antiferromagnetic ordering below TN = 8 K. The Curie–Weiss fit (200–350 K) gives a Curie–Weiss temperature of −42 K suggesting a dominant antiferromagnetic coupling in the Co2+ magnetic sublattices.

A new member of the descloizite family, a cobalt vanadate, SrCo(VO4)(OH), has been synthesized as large single crystals using high-temperature and high-pressure hydrothermal methods. SrCo(VO4)(OH) crystallizes in the orthorhombic crystal system in space group P212121 with the following unit cell parameters: a = 6.0157(2) A, b = 7.645(2) A, c = 9.291(3) A, V = 427.29(2) A3, and Z = 4. It contains one-dimensional Co-O-Co chains of edge-sharing CoO6 octahedra along the a-axis connected to each other via VO4 tetrahedra along the b-axis forming a three-dimensional structure. The magnetic susceptibility of SrCo(VO4)(OH) indicates an antiferromagnetic transition at 10 K as well as unusually large spin orbit coupling. Single-crystal magnetic measurements in all three main crystallographic directions displayed a significant anisotropy in both temperature- and field-dependent data. Single-crystal neutron diffraction at 4 K was used to characterize the magnetically ordered state. The Co2+ magnetic spins are arranged in a staggered configuration along the chain direction, with a canting angle that follows the tipping of the CoO6 octahedra. The net magnetization along the chain direction, resulting in ferromagnetic coupling of the a-axis spin components in each chain, is compensated by an antiferromagnetic interaction between nearest neighbor chains. A metamagnetic transition appears in the isothermal magnetization data at 2 K along the chain direction, which seems to correspond to a co-alignment of the spin directions of the nearest neighbor chain. We propose a phenomenological spin Hamiltonian that describes the canted spin configuration of the ground state and the metamagnetic transition in SrCo(VO4)(OH).

A novel technique for the absolute stereochemical determination of alcohols has been developed that uses crystallization of guanidinium salts of organosulfates. The simple one-pot, two-step process leverages facile formation of guandinium organosulfate single crystals for the straightforward determination of the absolute stereochemistry of enantiopure alcohols by means of X-ray crystallography. The strong hydrogen bonding network drives the stability of the crystal lattice and allows for a diverse range of organic alcohol substrates to be analyzed.

Materials with triangular arrangements of transition metal ions are of great interest for their complex magnetism resulting from geometric frustration. This paper describes the stepwise formation of kagome lattices of open shell transition-metal ions from half-delta chains to delta/sawtooth chains, and finally kagome nets. The systems can be viewed as a testbed for magnetic studies since a variety of spin states can be introduced across the same structure type, and progress through increasing levels of structural complexity and dimensionality. The synthetic and structural development of this continuum is studied here in well-formed single crystals of A2 M3 (MoO4 )3 (OH)2 (A=K, Rb; M=Mn, Co), CsM2 (MoO4 )2 (OH) (M=Mn, Fe, Co, Zn), and KM3 (MoO4 )2 O(OH) (M=Mn).

A hydrothermal route to single crystals of rare earth stannates RE2Sn2O7 (RE = La–Lu) in the cubic pyrochlore structure is reported. Growth reactions were performed in aqueous fluids at 700 °C and 200 MPa with CsF mineralizers in concentrations ranging from 0 to 30 M, with 20 M CsF providing the most consistent results. Single crystals of the entire range of lanthanides were grown and characterized by single crystal X-ray diffraction and found to be isostructural in the Fd3m space group. The unit cell sizes range from 10.7106(16) A for La2Sn2O7 to 10.3005(9) A for Lu2Sn2O7. Both the unit cell size and RE–O distances are found to be essentially linear with respect to the ionic radius of the rare earth ion. The high quality diffraction data strongly suggests that there is very little site disorder or lattice defects in the sample. Of particular interest is the synthesis and single crystal growth of Ce2Sn2O7, which represents one of the few f1 pyrochlore samples. Specific heat measurements were obtained dow...

The reactions of Ln2O3 (Ln = La Lu) with ReO2 were examined in high temperature hydrothermal water (650 °C). In all cases the rhenium oxide was added in a three-fold excess. No external mineralizer was needed and the rhenate itself acted as a sufficient mineralizer to form high quality single crystals of several crystalline products. These form in good yield with compositions varying as a function of the size of the rare earth ion. The largest sesquioxide, La2O3, forms the well-known La4Re6O19 phase, but when Ln = Nd or Pr, a new product, Ln2Re2O7(OH), is isolated. Reactions with Ln = Sm Tb form Ln4Re2O11, and those with Dy Lu form Ln2ReO5. The new Ln2Re2O7(OH) series was characterized as a new structure type by single crystal X-ray diffraction. This structure features a tetrameric Re4O16 cluster embedded in a lanthanide oxide framework. Additional detailed structural data is also provided for Tb4Re2O11 and Eu4Re2O11, which were not previously reported for the Ln4Re2O11 family. In Ln2Re2O7(OH), no direct Re Re bond (Re Re = 2.60 A) is observed while Ln4Re2O11 appears to possess a rhenium-rhenium double bond with a Re Re distance of 2.42 A. Single crystal Raman data supports both of these characterizations. Magnetic data is reported for Ln2Re2O7(OH) and Tb4Re2O11, and their behavior appears to be dominated by the f-element magnetic moments. At low temperatures Tb4Re2O11 displays possible canted antiferromagnetic coupling.

Two new structurally related cesium manganese vanadates have been synthesized by a high-temperature (580 °C) hydrothermal synthetic method utilizing halide brine mineralizers. Both structures Cs6Mn(H2O)2(VO3)8 (I) and Cs5KMn(H2O)2(VO3)8 (II) are isostructural crystallizing in the tetragonal space group P4/mnc. The first structure, Cs6Mn(H2O)2(VO3)8 (I) has unit cell dimensions of a = 13.6830(4) A, c = 8.6476(3) A and the second structure, Cs5KMn(H2O)2(VO3)8 (II), has unit cell dimensions of a = 13.5015(4) A, c = 8.5372(3) A. The structures are built from a manganese vanadate chain, which consists of [Mn(H2O)2O4] units that are coordinated to one another by a unique sinusoidal vanadate chain, (VO3)n. Both structures have well-ordered alkali metal atoms, with the potassium atoms of II exhibiting preferential site occupancy. Both compounds were characterized by single crystal X-ray diffraction and infrared spectroscopy, to identify the characteristic O–H and V–O modes. Crystals of Cs6Mn(H2O)2(VO3)8 and Cs5KMn(H2O)2(VO3)8 were synthesized from hydrothermal brines and their structures determined by single crystal X-ray diffraction, revealing preferential, ordered site substitution of the alkali metals.

Two new structural types of BaREGeO4(OH) and BaRE10(GeO4)4O8 (RE = Ho3+,Er3+) single crystals were synthesized via high-temperature and high-pressure hydrothermal synthesis. The BaREGeO4(OH) compounds were found to crystallize in the orthorhombic space group Pbca. BaHoGeO4(OH) is used as a representative of the family with cell parameters of a = 5.7175(2) A, b = 10.1556(5) A, c = 10.6189(9) A and V = 964.97(8) A3. The BaREGeO4(OH) structure contains a one-dimensional chain of rare-earth polyhedra linked through edge sharing of oxygen atoms. High density BaRE10(GeO4)4O8 crystals crystallize in the monoclinic space group C2/m and feature a sheet like arrangement of rare-earth oxide polyhedra with Keggin-like features. BaHo10(GeO4)4O8 is used as a representative of this structure type with cell parameters of a = 12.4533(8) A, b = 7.2008(5) A, c = 12.0034(8) A, β = 100.183(2)⁰ and V = 1059.43(12) A3. Barium polyhedra and isolated GeO4 units aid in connecting the rare earth oxide framework to extend it in three-dimensional (3-D) space. Characterization by single crystal X-ray diffraction and Raman and photoluminescence spectroscopies is reported.

The magnetic properties are reported for three members of the glaserite series of compounds, Na2BaM(VO4)2, M = Mn, Mn0.6Co0.4, and Co. Large single crystals are grown using a high-temperature hydrothermal synthesis method. This structure type exhibits a triangular magnetic lattice in which M2+O6 octahedra are interconnected with nonmagnetic (VO4)3- groups. All the structures crystallize at room temperature with rigid trigonal symmetry (space group P3 m1); however, at lower temperatures both Na2BaMn(VO4)2 and Na2BaMn0.6Co0.4(VO4)2 undergo a structural transition to lower symmetry (monoclinic, C2/ c). The bulk magnetic measurements indicate that Mn- and Co-structures are antiferromagnetic and ferromagnetic, respectively. Na2BaMn0.6Co0.4(VO4)2 does not show any long-range ordering down to 0.5 K, although a broad heat capacity anomaly near 1.2 K suggests short-range magnetic order or freezing into a spin-glass-like state related to the chemical disorder and resulting competing magnetic interactions. The magnetic structures of Na2BaMn(VO4)2 and Na2BaCo(VO4)2 were determined using neutron powder diffraction. At zero magnetic field, Na2BaMn(VO4)2 possesses an antiferromagnetic structure with the moments ordered in a Neel-type arrangement and aligned along the C4 axis of the octahedra. Under applied magnetic field at 0.3 K, the evolution of the magnetic structure toward a fully polarized state is observed. Na2BaCo(VO4)2 represents a ferromagnetic (FM) magnetic structure with Co moments aligned parallel to the c-axis direction. The relationships between these structures and magnetic properties are discussed.

Single crystals of a new transition metal adelite-descloizite-type structure were synthesized using a high temperature (580 °C) high-pressure hydrothermal technique. Single crystal X-ray diffraction and energy dispersive X-ray analysis (EDX) were used to investigate the structure and elemental composition, respectively. SrNi(VO4)(OH) crystallizes in an acentric orthorhombic crystal system in the space group P212121 (no. 19); Z = 4, a = 5.9952(4) Å, b = 7.5844(4) Å, c = 9.2240(5) Å. The structure is comprised of a Ni–O–V framework where Sr2+ ions reside inside the channels. Single-crystal magnetic measurements display a significant anisotropy in both temperature- and field-dependent data. The temperature dependent magnetic measurement shows antiferromagnetic behavior at TN~8 K. Overall, the magnetic properties indicate the presence of competing antiferromagnetic and ferromagnetic interactions of SrNi(VO4)(OH).

X-ray excited optical luminescence from nanophosphors can be used to selectively generate light in tissue for imaging and stimulating light-responsive materials and cells. Herein, we synthesized X-ray scintillating NaGdF

We report the latest progress on fabrication of rare earth doped single crystal yttrium aluminum garnet (YAG) core/undoped YAG cladded fibers. Rare-earth doped single crystal core fibers were grown with laser heated pedestal growth methods. In a second step, epitaxial methods were used to grow a single crystalline undoped YAG cladding onto the core fiber. Hydrothermal and liquid phase epitaxy methods utilize the core doped fiber as the seed. X-ray diffraction of cladding reveals an equilibrium (110) morphology. Energy-dispersive X-ray spectroscopy analysis shows there is minimal diffusion of rare-earth dopants into the cladding structure. The use of scandium doping is shown to substitute at the Al3+ site, thereby allowing an additional tunability of refractive index of core structure material besides conventional Y3+ site dopants. The use of these epitaxial growth methods enables material compatibility, tuning of refractive index, and conformal growth of cladding structures onto core fibers for optical devices.

A high temperature reactor was developed to synthesize new scintillating nanoparticles that traditionally would sinter. Yttrium pyrosilicate nanoparticles were synthesized with optical properties suitable for x-ray biomedical applications.

An examination of manganese silicates and germanates revealed unusual structural motifs and extremely different chemistries, with identical hydrothermal reactions forming K

Spin-$1/2$ antiferromagnetic triangular lattice models are paradigms of geometrical frustration, revealing very different ground states and quantum effects depending on the nature of anisotropies in the model. Due to strong spin orbit coupling and crystal field effects, rare-earth ions can form pseudospin-$1/2$ magnetic moments with anisotropic single-ion and exchange properties. Thus, rare-earth-based triangular lattices enable the exploration of this interplay between frustration and anisotropy. Here we study one such case, the rare-earth double vanadate glaserite material ${\mathrm{K}}_{3}\mathrm{Er}{({\mathrm{VO}}_{4})}_{2}$, which is a quasi-two-dimensional (2D) isosceles triangular antiferromagnet. Our specific heat and neutron powder diffraction data from ${\mathrm{K}}_{3}{\mathrm{Er}(\mathrm{VO}}_{4}{)}_{2}$ reveal a transition to long range magnetic order at ${T}_{N}=155\ifmmode\pm\else\textpm\fi{}5$ mK which accounts for all $Rln2$ entropy. We observe what appears to be a coexistence of three-dimensional (3D) and quasi-2D order below ${T}_{N}$. The quasi-2D order leads to an anisotropic Warren-like peak profile for $(hk0)$ reflections, while the 3D order is best-described by layers of antiferromagnetic $b$-aligned moments alternating with layers of zero moment. Our magnetic susceptibility data reveal that ${\mathrm{Er}}^{3+}$ takes on a strong $XY$ single-ion anisotropy in ${\mathrm{K}}_{3}\mathrm{Er}{({\mathrm{VO}}_{4})}_{2}$, leading to vanishing moments when pseudospins are oriented along $c$. Thus, the magnetic structure, when considered from the pseudospin point of view could comprise of alternating layers of $b$-axis and $c$-axis aligned antiferromagnetism.

Reactions are reported of early rare earth oxides, RE2O3 (RE = La, Pr, Nd) with Ta2O5 under hydrothermal conditions (650 °C, 1.5 kbar) in concentrated aqueous hydroxide (20-30 M KOH) as a mineralizer. Under various stoichiometries several members of two new structure types were isolated, Ln2TaO5(OH) (Ln = La, Pr) and Ln3Ta2O9(OH) (Ln = Pr, Nd). The analogous niobate La2NbO5(OH) was also obtained. Both structure types were characterized by single crystal X-ray diffraction and contain pentavalent tantalatum oxide octahedra and complex rare earth oxide frameworks. The Ln2TaO5(OH) structure type contains Ln-O8 and Ln-O9 building blocks and TaO6 octahedra in a 3-D framework. It contains a 3-D rare earth oxide framework formed by from zig-zag chains of rare earth oxides linking sheets of rare earth oxides. The tantalates form edge-shared Ta2O10 dimers occupying gaps in the rare earth oxide frameworks. The structure of Ln3Ta2O9(OH) contains two types of 2-D rare earth oxide slabs built of seven and eight coordinate rare earth metals. The tantalate units form 2-D slabs through a multiple corner-sharing scheme of TaO6 octahedra. The Ln3Ta2O9(OH) structure type has an interesting close structural relationship to the previously reported rare earth titanate La5Ti4O15(OH), which is discussed. The presence of hydroxide in the lattice is confirmed by IR spectroscopy and the H atom locations are assigned unambiguously using bond valence sums.

Two new alkali vanadate carbonates with divalent transition metals have been synthesized as large single crystals via a high-temperature (600 °C) hydrothermal technique. Compound I, Rb2Mn3(VO4)2CO3, crystallizes in the trigonal crystal system in the space group P3[combining macron]1c, and compound II, K2Co3(VO4)2CO3, crystallizes in the hexagonal space group P63/m. Both structures contain honeycomb layers and triangular lattices made from edge-sharing MO6 octahedra and MO5 trigonal bipyramids, respectively. The honeycomb and triangular layers are connected along the c-axis through tetrahedral [VO4] groups. The MO5 units are connected with each other by carbonate groups in the ab-plane by forming a triangular magnetic lattice. The difference in space groups between I and II was also investigated with Density Functional Theory (DFT) calculations. Single crystal magnetic characterization of I indicates three magnetic transitions at 77 K, 2.3 K, and 1.5 K. The corresponding magnetic structures for each magnetic transition of I were determined using single crystal neutron diffraction. At 77 K the compound orders in the MnO6-honeycomb layer in a Néel-type antiferromagnetic orientation while the MnO5 triangular lattice ordered below 2.3 K in a colinear 'up-up-down' fashion, followed by a planar 'Y' type magnetic structure. K2Co3(VO4)2CO3 (II) exhibits a canted antiferromagnetic ordering below TN = 8 K. The Curie-Weiss fit (200-350 K) gives a Curie-Weiss temperature of -42 K suggesting a dominant antiferromagnetic coupling in the Co2+ magnetic sublattices.

We present new high-resolution absorption data for the important sesquioxide laser material Yb:Lu2O3 for the spectral range of 880–1020 nm, at various temperatures between 8 and 300 K, and for the zero-phonon region from 960 to 990 nm, at temperatures from 8 to 300 K. We have experimentally observed the C3i (0,1)–(1,3) transition for the first time, located at 880.7 nm at 8 K. Based on high confidence fitting functions to the experimental data, we provide the first complete compilation of all observed electronic and electronic–vibrational transitions. Detailed fitting and plots of the C2 and C3i zero-line data show an evolution of the linewidth from being predominantly electronic below about 100 K to being dominated by thermal processes above 100 K. We have also found evidence for a “soft” phase transition between 80 and 100 K that changes the local coordination environment.

The macroscopic magnetic properties and microscopic magnetic structure of ${\mathrm{Rb}}_{2}{\mathrm{Mn}}_{3}{({\mathrm{MoO}}_{4})}_{3}{(\mathrm{OH})}_{2}$ (space group $Pnma)$ are investigated by magnetization, heat capacity, and single-crystal neutron diffraction measurements. The compound's crystal structure contains bond-alternating ${[{\mathrm{Mn}}_{3}{\mathrm{O}}_{11}]}^{\ensuremath{\infty}}$ chains along the $b$ axis, formed by isosceles triangles of Mn ions occupying two crystallographically nonequivalent sites (the Mn1 site on the base and Mn2 site on the vertex). These chains are only weakly linked to each other by nonmagnetic oxyanions. Both superconducting quantum interference device magnetometry and neutron diffraction experiments show two successive magnetic transitions as a function of temperature. On cooling, it transitions from a paramagnetic phase into an incommensurate phase below 4.5 K with a magnetic wave vector near ${\mathbf{k}}_{1}=(0,\phantom{\rule{0.16em}{0ex}}0.46,\phantom{\rule{0.16em}{0ex}}0)$. An additional commensurate antiferromagnetically ordered component arises with ${\mathbf{k}}_{2}=(0,\phantom{\rule{0.16em}{0ex}}0,\phantom{\rule{0.16em}{0ex}}0)$, forming a complex magnetic structure below 3.5 K with two different propagation vectors of different stars. On further cooling, the incommensurate wave vector undergoes a lock-in transition below 2.3 K. The experimental results suggest that the magnetic superspace group is $Pnma.{1}^{\ensuremath{'}}(0b0)s0ss$ for the single-$\mathbf{k}$ incommensurate phase and is $P{n}^{\ensuremath{'}}ma(0b0)00s$ for the two-$\mathbf{k}$ magnetic phase. We propose a simplified magnetic structure model taking into account the major ordered contributions, where the commensurate ${\mathbf{k}}_{2}$ defines the ordering of the $c$-axis component of the Mn1 magnetic moment, while the incommensurate ${\mathbf{k}}_{1}$ describes the ordering of the $ab$-plane components of both Mn1 and Mn2 moments into elliptical cycloids.

The current effort demonstrates that lutetium oxyorthosilicate doped with 1–10% cerium (Lu2SiO5:Ce, LSO:Ce) radioluminescent particles can be coated with a single dye or multiple dyes and generate an effective energy transfer between the core and dye(s) when excited via X-rays. LSO:Ce particles were surface modified with an alkyne modified naphthalimide (6-piperidin-1-yl-2-prop-2-yn-1-yl-1H-benzo[de]isoquinoline-1,3-(2H)-dione, AlNap) and alkyne modified rhodamine B (N-(6-diethylamino)-9-{2-[(prop-2-yn-1-yloxy)carbonyl]phenyl}-3H-xanthen-3-ylidene)-N-ethylethanaminium, AlRhod) derivatives to tune the X-ray excited optical luminescence from blue to green to red using Forster Resonance Energy Transfer (FRET). As X-rays penetrate tissue much more effectively than UV/visible light, the fluorophore modified phosphors may have applications as bioimaging agents. To that end, the phosphors were incubated with rat cortical neurons and imaged after 24 h. The LSO:Ce surface modified with AlNap was able to be success...

Large single crystals of Yb2Ge2O7 in the cubic Fd3m space group, are synthesized and characterized from a high-temperature hydrothermal method (650°C/200 MPa in 1 M KF). The cubic phase displays spin frustration and possibly nonclassical quantum-spin behavior at low temperature. This is the first report of single crystals of this important phase of size and quality suitable for single-crystal neutron diffraction.

The growth of large high quality single crystals of three lithium silicates and germanates Li 2 SiO 3 , Li 2 SiO 5 , and Li 2 GeO 3 is described. The crystals are all grown using hydrothermal fluids at 650 °C and 1 kbar using simple oxide feedstock and 3–6 M LiOH serving as both the lithium ion source and mineralizer. The crystals could be grown by spontaneous transport without any specific seeding, and grew between 2 and 10 mm/edge and without evidence of cracking, physical twinning or multiple domain structures. The crystals were characterized by single crystal diffraction, UV–vis spectroscopy and Raman spectroscopy. All the crystals are acentric and polar. Preliminary nonlinear optical properties were investigated using the Kurtz method and indicate that the crystals exhibit Type-1 phase matching ability, and Li 2 SiO 3 demonstrates a significant nonlinear optical conversion efficiency, making it of potential interest as a UV NLO crystal.

The proximity of minerals found in human hard tissues may influence cell phenotype. Since cells respond to a range of environmental cues, this study sought to identify the influence of two apatite-based microparticles, hydroxyapatite (HA) and fluoroapatite (FA), upon dental and bone cells. After bone marrow stromal cells (BMSCs), 7F2 osteoblasts and dental pulp stem cells (DPSCs) were plated into media with or without HA or FA particles, the cells were analyzed for alkaline phosphatase (ALP) production, collagen I production, osteocalcin production, and mineralization for two weeks. The BMSCs and DPSCs in media without any microparticles produced more ALP compared to those with microparticles from Day 5 forward. In addition, the collagen I and osteocalcin production in cultures without microparticles was higher than in cultures containing either HA or FA particles. While some studies have shown increased osteogeonic differentiation in the presence of mineral particles, those studies used nanoparticles that were able to be internalized by the cells and were smaller than the microparticles used in this study.

The structure of Cs3 RESi6 O15 , where RE=Dy-Lu, Y, In, is unusual in that it contains octahedrally coordinated rare-earth ions; their relative orientation dictates the structure, as they rotate about the c-axis supported by the cyclic Si6 O15 framework. The repeat unit of the rotation is eight units generating a very long (ca. 57 A) unit cell axis. This unusual repeat unit is created by the structural flexibility of the hexasilicate ring, which is in turn affected by the size of the rare earth ion as well as the size of alkali ion residing within the silicate layers. Previous work showed for the smaller Sc3+ ion, the rotation of the octahedra is not sufficient to achieve closure at an integral repeat unit and an incommensurate structure results. The products are prepared as large, high quality single crystals using a high-temperature (650 °C) hydrothermal method with CsOH and F- mineralizers. The presence of fluoride is essential to the formation of the product.

Reactions of rare-earth oxides with TiO2 were performed in high temperature (650–700 °C) hydrothermal fluids. Two different mineralizer fluids were examined, 20 M KOH and 30 M CsF, and their respective products analyzed. When concentrated KOH fluids were used, single crystals of a variety of new OH− containing species were isolated and structurally characterized: RE5Ti4O15(OH) (RE = La, Er) I, Sm3TiO5(OH)3II and RE5Ti2O11(OH) (RE = Tm–Lu) III. La5Ti4O15(OH) I crystallizes in the orthorhombic space group Pnnm with unit cell dimensions of a = 30.5152(12) A, b = 5.5832(2) A, c = 7.7590(3) A and V = 1321.92(9) A3, Z = 4. Sm3TiO5(OH)3II crystallizes in the monoclinic space group P21/m with unit cell parameters of a = 5.6066(2) A, b = 10.4622(4) A, c = 6.1258(2) A and β = 104.7390(10)°, V = 347.50(2) A3, Z = 2. Lu5Ti2O11(OH) III crystallizes in the monoclinic space group C2/m with unit cell dimensions of a = 12.1252(9) A, b = 5.8243(4) A, c = 7.0407(5) A, β = 106.939(3)° and V = 475.65(6) A3, Z = 2. When concentrated fluoride solutions are used, mostly RE2Ti2O7 type compounds were isolated in either cubic or monoclinic phases. In the case of cerium, Ce2Ti4O11IV was isolated that crystallizes in the monoclinic space group C2/c with unit cell parameters of a = 13.6875(7) A, b = 5.0955(3) A, c = 12.8592(7) A, β = 108.964(2)° and V = 848.18(8) A3, Z = 4. The synthesis, structural characterization, and supporting characterization are reported for all compounds. The work highlights the complementary nature of hydroxide and fluoride fluids in studying the reactivity of refractory oxides.

Two new halide-containing cesium manganese vanadates have been synthesized by a high-temperature (580 °C) hydrothermal synthetic method from aqueous brine solutions. One compound, Cs3Mn(VO3)4Cl, (1) was prepared using a mixed cesium hydroxide/chloride mineralizer, and crystallizes in the polar noncentrosymmetric space group Cmm2, with a = 16.7820(8) A, b = 8.4765(4) A, c = 5.7867(3) A. This structure is built from sinusoidal zig-zag (VO3)n chains that run along the b-axis and are coordinated to Mn2+ containing (MnO4Cl) square-pyramidal units that are linked together to form layers. The cesium cations reside between the layers, but also coordinate to the chloride ion, forming a cesium chloride chain that also propagates along the b-axis. The other compound, Cs2Mn(VO3)3F, (2) crystallizes in space group Pbca with a = 7.4286(2) A, b = 15.0175(5) A, c = 19.6957(7) A, and was prepared using a cesium fluoride mineralizer. The structure is comprised of corner sharing octahedral Mn2+ chains, with trans fluoride ligands acting as bridging units, whose ends are capped by (VO3)n vanadate chains to form slabs. The cesium atoms reside between the manganese vanadate layers, and also play an integral part in the structure, forming a cesium fluoride chain that runs along the b-axis. Both compounds were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and single-crystal Raman spectroscopy. Additionally, the magnetic properties of 2 were investigated. Above 50 K, it displays behavior typical of a low dimensional system with antiferromagnetic interactions, as to be expected for linear chains of manganese(ii) within the crystal structure.

The structural and magnetic properties of a glaserite-type Na2BaFe(VO4)2 compound, featuring a triangular magnetic lattice of Fe2+ (S = 2), are reported. Temperature dependent X-ray single crystal studies indicate that at room temperature the system adopts a trigonal P3m1 structure and undergoes a structural phase transition to a C2/c monoclinic phase slightly below room temperature (Ts = 288 K). This structural transition involves a tilting of Fe-O-V bond angles and strongly influences the magnetic correlation within the Fe triangular lattice. The magnetic susceptibility measurements reveal a ferromagnetic transition near 7 K. Single crystal neutron diffraction confirms the structural distortion and the ferromagnetic spin ordering in Na2BaFe(VO4)2. The magnetic structure of the ordered state is modeled in the magnetic space group C2'/c' that implies a ferromagnetic order of the a and c moment components and antiferromagnetic arrangement for the b components. Overall, the Fe magnetic moments form ferromagnetic layers that are stacked along the c-axis, where the spins point along one of the (111) facets of the FeO6 octahedron.

Three new strontium manganese vanadates, Sr 2 Mn 2 (V 3 O 10 )(VO 4 ) ( I ), Sr 3 Mn(V 2 O 7 ) 2 ( II ), and Sr 2 Mn(VO 4 ) 2 (OH) ( III ), were prepared using a high temperature (580 °C) hydrothermal method with various chloride salts as the mineralizer. Minor differences in the chloride stoichiometry led to significant differences in product. Compound I crystallizes in the monoclinic space group P 2 1 / c ( a = 6.8773(12) A, b = 15.061(3) A, c = 11.609(2) A, β = 96.745(8)°), and consists of edge-shared octahedral manganese(II) dimers coordinated by trimeric [V 3 O 10 ] and monomeric [VO 4 ] groups. Compound II crystallizes in the tetragonal crystal system, P 4 3 2 1 2 ( a = 6.9951(2) A, c = 25.4390(7) A), and is built from monomeric manganese(II) octahedra chelated by two pyrovanadate [V 2 O 7 ] groups and linked to each other by additional pyrovanadates to form layers. Compound III is a noncentrosymmetric variation on the brackebuschite structure type, crystallizing in the monoclinic space group P 2 1 ( a = 7.6316(3) A, b = 6.1204(3) A, c = 8.6893(3) A, β = 111.3940(10)°). The structure is composed of octahedral manganese(III) edge-sharing chains coordinated to corner-sharing monomeric [VO 4 ] groups, thereby forming a manganese vanadate chain. All compounds were characterized by single-crystal X-Ray diffraction, powder X-Ray diffraction, infrared spectroscopy and single-crystal Raman spectroscopy. Density functional theory calculations were employed to investigate the relative stability of compound III .

Structural variations across a series of barium rare earth (RE) tetrasilicates are studied. Two different formulas are observed, namely those of a new cyclo-silicate fluoride, BaRE2Si4O12F2 (RE = Er3+–Lu3+) and new compounds in the Ba2RE2Si4O13 (RE = La3+–Ho3+) family, covering the whole range of ionic radii for the rare earth ions. The Ba2RE2Si4O13 series is further subdivided into two polymorphs, also showing a dependence on rare earth ionic radius (space group P{\overline 1} for La3+–Nd3+, and space group C2/c for Sm3+–Ho3+). Two of the structure types identified are based on dinuclear rare earth units that differ in their crystal chemistries, particularly with respect to the role of fluorine as a structural director. The broad study of rare earth ions provides greater insight into understanding structural variations within silicate frameworks and the nature of f-block incorporation in oxyanion frameworks. The single crystals are grown from high-temperature (ca 953 K) hydrothermal fluids, demonstrating the versatility of the technique to access new phases containing recalcitrant rare earth oxides, enabling the study of structural trends.

Two terbium germanates have been synthesized via high-temperature and high-pressure hydrothermal synthesis with 20 M KOH as a mineralizer using Tb4O7 as a starting material. Tb13(GeO4)6O7(OH) crystallizes in trigonal space group R3, is built up of isolated GeO4 units, and contains a complex arrangement of terbium oxide polyhedra. K2TbGe2O7 is a terbium(4+) pyrogermanate that is isostructural with K2ZrGe2O7 and displays a rare stable Tb4+ oxidation state in the solid state.

Recently, a local-Ising-type magnetic order was inferred from neutron diffraction of the antiferromagnetic ${\mathrm{Er}}_{2}{\mathrm{Ge}}_{2}{\mathrm{O}}_{7}$ (pg-ErGO) with an applied magnetic field. Here, we use neutron spectroscopy to investigate the energetics of pg-ErGO and the isostructural ${\mathrm{Yb}}_{2}{\mathrm{Ge}}_{2}{\mathrm{O}}_{7}$ (pg-YbGO) to evaluate the adequacy of the local-Ising description. To begin, we generate a model of the magnetic structure of pg-YbGO using neutron diffraction and find a net ferromagnetic moment. While pg-ErGO and pg-YbGO have highly symmetric crystal structures ($P{4}_{1}{2}_{1}2$ tetragonal space group 92) with only one trivalent rare-earth magnetic site, the point symmetry of the rare-earth site is low with only a single symmetry element (point group ${\mathrm{C}}_{1}$). For both compounds, the energy scale of the first excited state is large compared to the magnetic ordering temperature, suggesting Ising character. The ground-state Kramer's doublet of both compounds is dominated by the maximal ${m}_{\mathrm{J}}$ component. However, the low point group symmetry of the rare-earth site leads to finite mixing of all other ${m}_{\mathrm{J}}$'s, which suggests potential deviations from Ising behavior. Moreover, quasielastic scattering is observed deep in the ordered state of pg-ErGO and pg-YbGO that may be due to non-Ising behavior. The dominant magnetic interaction in both compounds is found to be magnetostatic by considering the magnetic excitations in the ordered state. From consideration of these data, the pg-YbGO is more Ising-like than pg-ErGO. Also, quantum multicritical points are anticipated with applied magnetic field in both compounds.

A new member of the descloizite family, a cobalt vanadate, SrCo(VO

Reactions are reported of early rare earth oxides, RE

Nanoparticle-based delivery systems have become a popular method for targeting tumors and impermeable tissue with drugs for treatment and imaging markers for biodetection. Nanomaterials are beneficial for medical treatment because they can be modified to have increased stability and carrying capacity, and their size and surface modifications allow them to reach otherwise impenetrable tissue. Nanoparticles have become particularly popular in medical imaging since they can be produced as scintillators that emit visible light which can be used in PET detectors, or they could be made with paramagnetic materials for magnetic resonance imaging. Localized or systemic injection can be used for delivery of nanoparticles; however, systemic injection without appropriate surface modifications is subjected to uptake by the mononuclear phagocytic system which clears particles from the circulation rapidly limiting their accumulation at target tissue and reducing efficacy. Here we demonstrate the biodistribution of Yttrium oxyorthosilicate nanoparticles doped with Cerium after localized injection to the cerebral cortex.

All-solid-state deep UV lasers (266nm and shorter) have many potential applications including metrology, LIBS, imaging, chem/bio standoff detection, ARPES spectroscopy, and laser surgery. There are few suitable direct laser emission lines at such short wavelengths, making the use of frequency generation by harmonic generation an important tool for UV solid state laser development. The primary limitation of the field is the development of suitable single crystals for nonlinear frequency conversion. The materials must be acentric, have bandgaps substantially wider than the desired conversion line and and be capable of phase matching to these short wavelengths. Several borate crystals have been reported as possible candidates for deep UV nonlinear applications. These include compounds with the formula ABBF (ABe2BO3F2) where A = K, Rb or Cs, and SBBO (Sr2Be2B2O7). Both compounds have very attractive properties for deep UV nonlinear applications including acentric crystal structures, wide band edges, moderate birefringence and reasonable nonlinear coefficients. Both classes are difficult to crystallize and process however. They have two dimensional structures making them somewhat soft, difficult to cut and polish at a critical angle, and making them prone to disorder. The ABBF phases have very attractive optical properties with wide bandgaps and are capable of frequency conversion to 175nm. They are extremely difficult to grow as single crystals however and are extremely soft and difficult to process. To date these are debilitating limitations. The SBBO crystals appear to have nearly as attractive properties with somewhat less of a bandgap than KBBF, but appear to have greater NLO coefficients. They are considerably harder than KBBF but are prone to severe disorder. Recently the application of hydrothermal methods led to the crystal growth of both of these classes of compounds. The hydrothermal growth of KBBF and RBBF led to formation of large single crystals that can be used for new cutting and polishing methods enabling their use in applications such as ARPES. The hydrothermal growth of SBBO greatly reduces the disorder in the crystals enabling a more confident determination of their optical properties. The recent structural redetermination of SBBO and the examination of their optical properties will be discussed.