Advances in Studies of Boron Nitride Nanosheets and Nanocomposites for Thermal Transport and Related Applications.

Hexagonal boron nitride (h-BN) and exfoliated nanosheets (BNNs) not only resemble their carbon counterparts graphite and graphene nanosheets in structural configurations and many excellent materials characteristics, especially the ultra-high thermal conductivity, but also offer other unique properties such as being electrically insulating and extreme chemical stability and oxidation resistance even at elevated temperatures. In fact, BNNs as a special class of 2-D nanomaterials have been widely pursued for technological applications that are beyond the reach of their carbon counterparts. Highlighted in this article are significant recent advances in the development of more effective and efficient exfoliation techniques for high-quality BNNs, the understanding of their characteristic properties, and the use of BNNs in polymeric nanocomposites for thermally conductive yet electrically insulating materials and systems. Major challenges and opportunities for further advances in the relevant research field are also discussed.

Bright X-ray and up-conversion nanophosphors annealed using encapsulated sintering agents for bioimaging applications.

Nanophosphors are promising contrast agents for deep tissue optical imaging applications because they can be excited by X-ray and near infrared light that penetrates deeply through tissue and generates almost no autofluorescence background in the tissue. For these bioimaging applications, the nanophosophors should ideally be small, monodispersed and brightly luminescent. However, most methods used to improve luminescence yield by annealing the particles to reduce crystal and surface defects (e.g. using flux or sintering agents) also cause particle fusion or require multiple component core-shell structures. Here, we report a novel method to prepare bright, uniformly sized X-ray nanophosphors (Gd2O2S:Eu or Tb) and upconversion nanophosphors (Y2O2S: Yb/Er, or Yb/Tm) with large crystal domain size without causing aggregation. A core-shell nanoparticle is formed, with NaF only in the core. We observe that increasing the NaF sintering agent concentration up to 7.6 mol% increases both crystal domain size and luminescence intensity (up to 40% of commercial microphosphors) without affecting the physical particticle diameter. Above 7.6 mol%, particle fusion is observed. The annealing is insensitive to the cation (Na+ or K+) but varies strongly with anion, with F->Cl->CO32->Br->I-. The luminescence depends strongly on crystal domain size. The data agree reasonably well with a simple domain surface quenching model, although the size-dependence suggests additional quenching mechanisms within small domains. The prepared bright nanophosphors were subsequently functionalized with PEG-folic acid to target MCF-7 breast cancer cells which overexpress folic acid receptors. Both X-ray and upconversion nanophosphors provided low background and bright luminescence which was imaged through 1 cm chicken breast tissue at a low dose of nanophosphors 200 µL (0.1 mg/mL). We anticipate these highly monodispersed and bright X-ray and upconversion nanophosphors will have significant potential for tumor targeted imaging.

M3(P2O7)22--type open frameworks featuring [M2O8] and [M3O12] multinuclear transition-metal oxide units. Serendipitous synthesis of six polymorphic salt-inclusion magnetic solids: Na2M3(P2O7)2·ACl (M = Mn, Fe; A = Rb, Cs) and K2M3(P2O7)2·CsCl (M = Fe, Mn).

Single crystals of six polymorphic salt-inclusion phosphates of the A(2)M(3)(P(2)O(7))(2)·A'Cl type, Na(2)Mn(3)(P(2)O(7))(2)·CsCl (1), Na(2)Mn(3)(P(2)O(7))(2)·RbCl (2), Na(2)Fe(3)(P(2)O(7))(2)·CsCl (3), Na(2)Fe(3)(P(2)O(7))(2)·RbCl (4), K(2)Mn(3)(P(2)O(7))(2)·CsCl (5), and K(2)Fe(3)(P(2)O(7))(2)·CsCl (6), were grown in reactive molten chloride flux media. Compounds 1-4 are isostructural and crystallize in the space group C2/c (No. 15), while 5 and 6 crystallize in P2/c (No. 13) and P1̅ (No. 2), respectively. The title compounds have demonstrated an unprecedented versatility, where the M(3)(P(2)O(7))(2)(2-) covalent open frameworks contain [M(3)O(12)] (M = Mn(2+), Fe(2+)) trimeric units in 1-4 and [M(2)O(8)] dimers in 5 and 6. These multinuclear, transition-metal oxide units are linked by Cl(-) ions through the M-Cl bonds to form one-dimensional (1D) chains. The 1D chains and [P(2)O(7)] groups share common O atoms to form the extended network. The M(3)(P(2)O(7))(2)(2-) open-framework structures exhibit channels where the respective Na(+)/K(+) ions and A'Cl salt (A' = Rb, Cs) reside. Magnetic susceptibility of 2 and 4 suggests bulk antiferromagnetic properties as expected. The local structure and thermal decomposition are examined by IR and differential scanning calorimetry of representative compounds. The factors that determine the reticular chemistry of the M(3)(P(2)O(7))(2)(2-) type are illustrated in terms of the inclusion of ionic lattices of different sizes and contents.

Iron-Loaded Magnetic Nanocapsules for pH-Triggered Drug Release and MRI Imaging.

Magnetic nanocapsules were synthesized for controlled drug release, magnetically assisted delivery, and MRI imaging. These magnetic nanocapsules, consisting of a stable iron nanocore and a mesoporous silica shell, were synthesized by controlled encapsulation of ellipsoidal hematite in silica, partial etching of the hematite core in acid, and reduction of the core by hydrogen. The iron core provided a high saturation magnetization and was stable against oxidation for at least 6 months in air and 1 month in aqueous solution. The hollow space between the iron core and mesoporous silica shell was used to load anticancer drug and a T1-weighted MRI contrast agent (Gd-DTPA). These multifunctional monodispersed magnetic "nanoeyes" were coated by multiple polyelectrolyte layers of biocompatible poly-l-lysine and sodium alginate to control the drug release as a function of pH. We studied pH-controlled release, magnetic hysteresis curves, and T1/T2 MRI contrast of the magnetic nanoeyes. They also served as MRI contrast agents with relaxivities of 8.6 mM-1 s-1 (r1) and 285 mM-1 s-1 (r2).

Multifunctional yolk-in-shell nanoparticles for pH-triggered drug release and imaging.

Multifunctional nanoparticles are synthesized for both pH-triggered drug release and imaging with radioluminescence, upconversion luminescent, and magnetic resonance imaging (MRI). The particles have a yolk-in-shell morphology, with a radioluminescent core, an upconverting shell, and a hollow region between the core and shell for loading drugs. They are synthesized by controlled encapsulation of a radioluminescent nanophosphor yolk in a silica shell, partial etching of the yolk in acid, and encapsulation of the silica with an upconverting luminescent shell. Metroxantrone, a chemotherapy drug, was loaded into the hollow space between X-ray phosphor yolk and up-conversion phosphor shell through pores in the shell. To encapsulate the drug and control the release rate, the nanoparticles are coated with pH-responsive biocompatible polyelectrolyte layers of charged hyaluronic acid sodium salt and chitosan. The nanophosphors display bright luminescence under X-ray, blue light (480 nm), and near infrared light (980 nm). They also served as T1 and T2 MRI contrast agents with relaxivities of 3.5 mM(-1) s(-1) (r1 ) and 64 mM(-1) s(-1) (r2 ). These multifunctional nanocapsules have applications in controlled drug delivery and multimodal imaging.

Synthesis and structure of bismuth(III)-containing noncentrosymmetric phosphates, Cs3KBi2M4(PO4)6Cl (M = Mn, Fe). Monoclinic (Cc) and tetragonal (P43) polymorphs templated by chlorine-centered Cl(Bi2Cs) acentric units.

Single crystals of three new noncentrosymmetric (NCS) phosphates, α (1) and ß (2) forms of Cs(3)KBi(2)Mn(4)(PO(4))(6)Cl and α-Cs(3)KBi(2)Fe(4)(PO(4))(6)Cl (3), were grown in a reactive CsCl/KCl molten-salt media. Their structures were determined by single-crystal X-ray diffraction methods showing that the α form crystallizes in the space group Cc (No. 9), which is in one of the 10 NCS polar crystal classes, m (2/m) while the ß form crystallizes in P4(3) (No. 78) of another polar class, 4 (4/m). The unit cell parameters of the α form can be approximately correlated with that of the ß form via the 3 × 3 orientation matrix [0.5, 0.5, 0; -0.5, 0.5, 0; 0, 0, 2 sin ß]. The structures of these otherwise complicated phosphates exhibit two types of channels with circular and elliptical windows where the Cl-centered Cl(Bi(2)Cs) acentric unit is located. The neighboring acentric units are arranged in a parallel fashion in the α form, resulting in the monoclinic (Cc) lattice, but "antiparallel" in the ß form, thus giving the tetragonal (P4(3)) unit cell. 1-3 feature the compatible M-O-P unit that contains four crystallographically independent MO(x) (x = 4, 5) polyhedra, which are connected to the Cl(Bi(2)Cs) acentric unit through one short and one long M(II)···Cl bond. The compositions of 1 and 2 consist of three Mn(2+) (d(5)) and one Mn(3+) (d(4)) per formula unit and that of 3 has three Fe(2+) (d(6)) and one Fe(3+) (d(5)). Bond valence sums reveal that, in the α phase, the trivalent site adopts distorted tetrahedral M(1)(3+)O(4) coordination and, in the ß phase, distorted trigonal-bipyramidal M(4)(3+)O(5). Thus far, the iron phase has only been isolated in the α form presumably because of little extra stabilization energy gain if the Fe(2+) d(6) ion were to occupy the M(1)O(4) site. The possible origins pertaining to the structural differences in the α and ß forms are discussed.

Symmetry preservation in a new noncentrosymmetric lattice comprised of acentric POM clusters residing in bowls of Cs(+)-based half SOD ß-cage.

In light of ever growing interests in noncentrosymmetric materials, a fascinating reticular chemistry is illustrated via the structure of a new family of solids where the acentric symmetry of the well-known [V(4+)(14)As(3+)(8)O(42)Cl](5-) POM cluster is manifested through the network construction of counter cations featuring slabs of Cs(+)-based half SOD ß-cages.

Extended utility of molten-salt chemistry: unprecedented synthesis of a water-soluble salt-inclusion solid comprised of high-nuclearity vanadium oxide clusters.

Polyoxometallates (POMs) are desirable in materials applications ranging from uses as catalysts in selective oxidation reactions to molecular-like building blocks for the preparation of new extended solids. With the use of an unprecedented approach involving high temperature, molten salt methods, a fascinating series of salt-inclusion solids (SISs) that contain high nuclearity POMs has been isolated for the first time. Cs(11)Na(3)(V(15)O(36))Cl(6) (1) was synthesized using the eutectic NaCl/CsCl flux (mp 493 °C) which serves as a reactive solvent in crystal growth and allows for the SIS formation. Its framework can be viewed as an "ionic" lattice composed of alternately packed counterions of Cl-centered [V(15)O(36)Cl](9-) clusters (V15; S = 11/2) and multinuclear [Cs(9)Na(3)Cl(5)](7+) cations. In light of the structural analysis, 1 was proven to be soluble in water giving rise to a dark green solution that is similar in color to single crystals of the title compound. Infrared spectroscopy of the solid formed from fast evaporation of the solution supports the presence of dissolved V15 clusters. Also noteworthy is the magnetization of 1 at 2 K, which reveals an s-shaped plot resembling that of superparamagnetic materials.

Evidence for surface states in pristine and Co-doped ZnO nanostructures: magnetization and nonlinear optical studies.

An unexpected presence of ferromagnetic (FM) ordering in nanostructured ZnO has been reported previously. Recently, from our detailed magnetization studies and ab initio calculations, we attributed this FM ordering in nanostructured ZnO to the presence of surface states, and a direct correlation between the magnetic properties and crystallinity of ZnO was observed. In this study, through a systematic sample preparation of both pristine and Co-doped ZnO nanostructures, and detailed magnetization and nonlinear optical (NLO) measurements, we confirm that the observed FM ordering is due to the presence of surface states.

Salt-templated mesoporous solids comprised of interlinked polyoxovanadate clusters.

The utility of molten salts has been demonstrated in the synthesis of the first family of mesoporous salt-inclusion solids featuring [V(4)O(16)] and [V(5)O(17)] polyoxovanadate (POV) units interlinked by As(5+) cations. Despite a high-temperature synthesis, these new solids exhibit unusually porous ( approximately 2-nm-diameter) vanadium arsenate frameworks. Disordered metal chloride salts reside inside the pores, leading to relatively large voids (up to approximately 7.2% of the unit cell volume), which were confirmed by surface area (SA) measurements of the as-prepared polycrystalline samples ( approximately 90-110 m(2)/g). Given the potential utility of porous POV-containing materials, efforts were made to study changes in the SAs (showing approximately 35-70% increases) upon salt removal and redox chemistry.

Synthesis, structure, and magnetic properties of Na3LnMn3O3(AsO4)3 (Ln = La, Sm, and Gd): a new 3d-4f series exhibiting one-dimensional manganese(III) oxide chains connected via LnO9 units.

In attempts to synthesize compounds containing mixed lanthanide and transition metal oxide magnetic nanostructures, a new 3d-4f arsenate phase, Na(3)GdMn(3)O(3)(AsO(4))(3), was isolated using high-temperature, molten-salt methods. The X-ray single-crystal structure analysis shows that Na(3)GdMn(3)O(3)(AsO(4))(3) crystallizes in a hexagonal space group with a = 11.091(2) A, c = 5.954(1) A, and V = 634.2(2) A(3); P6(3)/m (No.176); Z = 2. The structure has been refined by full-matrix, least-squares methods to a final solution with R1 = 0.0466, wR2 = 0.1318 and GOF = 1.101. This new three-dimensional framework consists of ferromagnetic one-dimensional [MnO(4)](infinity) chains, composed of edge-shared MnO(6) units propagating along c. The GdO(9) polyhedra connect three neighboring [MnO(4)](infinity) chains via oxygen atoms. Na(3)LaMn(3)O(3)(AsO(4))(3) (1), and Na(3)SmMn(3)O(3)(AsO(4))(3) (2), the isostructural derivatives of Na(3)GdMn(3)O(3)(AsO(4))(3) (3), were synthesized to acquire additional insight into the 3d-4f magnetic couplings. The Na(3)LnMn(3)O(3)(AsO(4))(3) series reveals an increase in chiT at low temperatures upon substitution of smaller Ln(3+) ions ranging from La(3+) to Gd(3+). The increase in chiT is likely due to the magnetic nature and size of the lanthanide ions present. It was expected that the Mn-O-Mn ferromagnetic interactions would dominate as 3d-4f magnetic interactions are generally weak. The magnetic data shows that the paramagnetic Ln(3+) ions in 2 (Sm) and 3 (Gd) do significantly enhance the bulk ferromagnetism compared to that of 1 (La), suggesting sizable contributions from the 4f magnetic ions.

New cuprates featuring ladderlike periodic arrays of [Cu3O8]10- trimeric magnetic nanostructures.

A new family of cuprates, Li2Cu3(SiO3)4 (1) and Na2Cu3(GeO3)4 (2), was isolated in molten salt media. The extended lattices contain ladderlike periodic arrays of [Cu3O8]10- magnetic nanostructures. Magnetic properties of the Na2Cu3Ge(4-x)SixO12 series, where x = 0, 0.86, and 1.72, were systematically studied. The geometrically induced magnetic couplings are tunable upon cation substitution.

Synthesis, structure, and magnetic properties of Cs(2-x)RbxCu3P4O14 (0.0

In our continued exploratory synthesis of compounds containing transition-metal oxide magnetic nanostructures, a new copper(II) phosphate phase, Cs2Cu3P4O14 (1), was isolated employing the mixed CsCl/2CsI molten flux. The X-ray single-crystal structural analysis shows that the Cs2Cu3P4O(14) phase crystallizes in a monoclinic space group with a = 7.920(2) A, b = 10.795(2) A, c = 7.796(2) A, beta = 103.90(3) degrees , and V = 646.9(2) A(3); P2(1)/c (No. 14); Z = 2. The structure has been refined by the full-matrix least-squares method to a final solution with R1 = 0.0248, wR2 = 0.0553, and GOF = 1.02. The three-dimensional Cu-O-P framework exhibits pseudo-one-dimensional channels where the Cs+ cations reside. The framework consists of trimeric CuO4 square-planar units stacked in a staggered configuration. These CuO4 trimers are interlinked by the P2O7 units via vertex-sharing O atoms. The stacked CuO4 units are slanted with respect to the Cu...Cu...Cu vector, resulting in additional Cu-O long bonds, 2.71(1) A, and a possibly shortened Cu...Cu distance, 3.38(3) A. 1 shows limited cation substitution with smaller alkali-metal cations; in fact, only a relatively small concentration of Cs+ can be substituted by Rb+ to form Cs(2-x)RbxCu3P4O14 (0.0

Salt-inclusion synthesis of two new polar solids, Ba6Mn4Si12O34Cl3 and Ba6Fe5Si11O34Cl3.

A new family of salt-containing, mixed-metal silicates (CU-14), Ba6Mn4Si12O34Cl3 (1) and Ba6Fe5Si11O34Cl3 (2), was synthesized via the BaCl2 salt-inclusion reaction. These compounds crystallize in the noncentrosymmetric (NCS) space group Pmc2(1) (No. 26), adopting 1 of the 10 NCS polar, nonchiral crystal classes, mm2 (C2v). The cell dimensions are a = 6.821(1) A, b = 9.620(2) A, c = 13.172(3) A, and V = 864.4(3) A3 for 1 and a = 6.878(1) A, b = 9.664(2) A, c = 13.098(3) A, and V = 870.6(3) A3 for 2. The structures form a composite framework made of the (M(4+x)Si(12-x)O34)9- (M = Mn, x = 0; M = Fe, x = 1) covalent oxide and (Ba6Cl3)9+ ionic chloride sublattices. The covalent framework exhibits a pseudo-one-dimensional channel where the extended barium chloride lattice (Ba3Cl1.5)(infinity) resides, and it consists of fused eight-membered meta-silicate rings propagating along [100] via sharing two opposite [Si2O7]6- units to form an acentric lattice. Single-crystal structure studies also reveal the ClBa4 unit adopting an interesting seesaw configuration, in which the lone pair electrons of chlorine preferentially face the oxide anions of the transition metal silicate channel, thus forming the observed polar frameworks. Similar to the synthesis of organic-inorganic hybrid materials, the salt-inclusion method facilitates a promising approach for the directed synthesis of special framework solids, including NCS compounds, via composite lattices.

Salt-inclusion synthesis of Ba2MnSi2O7Cl. A fresnoite-type polar framework containing the acentric [Si2O7]6 - polyanion in the anti-ReO3 type [(Ba2Mn)Cl]6+) cage.

A novel non-centrosymmetric (NCS) solid, Ba(2)Mn(Si(2)O(7))Cl (CU-13), was isolated via high-temperature, salt-inclusion reactions. This manganese(III) silicate chloride adopts the fresnoite structure exhibiting pseudo-one-dimensional channels in which the Ba(2+) cations reside. The framework can be viewed alternatively as made of a fascinating anti-ReO(3) type (Ba(2)Mn)Cl lattice centered on the acentric Si(2)O(7) unit. This new compound crystallizes in one of the 10 NCS polar crystal classes, 4mm (C(4)(v)()), which is cooperatively attributed to the MnO(4)Cl(2) tetragonal distortion and the oriented Si(2)O(7) polyhedral unit. This discovery once again demonstrates the utility of salt inclusion with the formation of NCS frameworks.

Nanostructured magnetic cuprate cluster: synthesis, structure, UV-Vis spectroscopy, and magnetic properties of a new copper(II) arsenate NaCuAsO4 containing discrete [Cu4O16]24- clusters.

Crystals of copper(II) arsenate NaCuAsO(4) were grown by conventional high-temperature, solid-state methods in molten-salt media. The compounds were characterized by single crystal X-ray diffraction, UV-vis spectroscopy, and magnetic susceptibility measurements. NaCuAsO(4) crystallizes in a monoclinic lattice with a = 6.002 (1) A, b = 10.853 (2) A, c = 10.373 (2) A, beta = 91.50 (3) degrees, and V = 675.4(2) A(3); P2(1)/c (No. 14); Z = 8. The newly isolated sodium copper(II) arsenate reveals a pseudo-one-dimensional channel structure where the sodium cations reside. The extended framework contains nanostructured [Cu(4)O(16)](24-) magnetic clusters that are interlinked by closed-shell, nonmagnetic AsO(4)(3-) oxy anions via sharing vertex oxygen atoms of the CuO(5) and AsO(4) polyhedral units. Each [Cu(4)O(16)](24-) cluster consists of four CuO(5) square pyramidal units in a chair configuration centered by a center of inversion. The two crystallographically independent Cu(2+) cations adopt the [4 + 1] CuO(5) Jahn-Teller distortion giving rise to an intense d-d transition in UV-vis absorption spectra. The magnetic susceptibility measurements reveal that the title compound is antiferromagnetic. At high temperatures, the data follows a pure Curie law, suggesting noninteracting spins, but with a rapid suppression of the effective spin below T = 70 K. At low temperature, the susceptibility collapses, indicating spin gap formation as the magnetic-cluster material settles into the lowest energy magnetic singlet state. The current work in the exploratory synthesis of oxy compounds containing nanostructured transition-metal-oxide magnetic clusters leads to new materials for experimental and theoretical developments of magnetic models.

The fascinating noncentrosymmetric copper(II) phosphates synthesized via CsCl salt-inclusion.

Two new noncentrosymmetric (NCS) solids were isolated via high-temperature, salt-inclusion reactions, Cs(2)Cu(7)(P(2)O(7))(4).6CsCl (1, CU-9) and Cs(2)Cu(5)(P(2)O(7))(3).3CsCl (2, CU-11). These copper(II) phosphates exhibit novel open-framework structures conceptually templated by extended Cs-Cl salt. The latter resides cooperatively in the channels upon the formation of the NCS Cu-P-O frameworks, leading to the formation of fascinating salt lattices centered by the NaCl-type core. These new discoveries are significant for they may give rise to a new route for the templated synthesis of NCS solids. We are to show here the structural correlation of the newly discovered hybrid solids, and the role of the chlorine atoms in the "intergrowth" of covalent/ionic sublattices.