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The optical and chemical properties of gold and silver nanoparticles make them useful for many applications, including surface enhanced spectroscopy‐based biosensors, photostable colorants, enhanced photovoltaic, and nanoscale optical elements. We report a simple technique to generate patterns of gold and silver nanoparticles with controlled shape and shape‐dependent optical properties using metal stamps to impress them onto a glass substrate or flexible polymers. The pressure flattens the nanoparticles, converting initially spherical nanoparticles into discs with reduced height and increased diameter. This deformation causes their localized surface plasmon resonance wavelength to red‐shift. Nanoparticles were characterized by electron microscopy, atomic force microscopy, and dark field optical scattering spectroscopy. The deformed nanoparticle patterns had a lateral resolution limited by the nanoparticle diameter (single particles are partly flattened only where they contact the stamp). The method also (i) transfers the stamp's topography, with smooth stamps generating flattened nanoparticles with uniform height, and small changes in stamp height are evident in the nanoparticle height and scattering wavelength, and (ii) allows facile removal of undeformed nanoparticles using scotch tape, and patterns of deformed nanoparticles can be transferred to a flexible polymer film. The patterning process is simple and inexpensive. It can be performed by hand for demonstrations or artistic applications, with controlled force for plasmonics research, and potentially automated on reel‐to‐reel presses for large scale production.

Plasmonic single-crystal silver nanoparticles exhibit high efficiency for the interaction with light and low intrinsic losses across the visible and near-infrared spectral ranges as manifested by w...

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 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 conversion of CO2 into useful chemicals can lead to the production of carbon neutral fuels and reduce greenhouse gas emissions. A key technological challenge necessary to enable such a process is the development of substrates that are active, cost effective, and selective for this reaction. In this regard, the reduction of CO2 via electrochemical means is one of the most attractive alternatives but still requires rather unique electrodes. Considering the potential of this approach, this report describes a one-step methodology for the synthesis of carbon electrodes derived from simple paper and modified with various metallic nanoparticles. Upon a preliminary selection based on the catalytic activity towards CO2 reduction, the electrodes containing CuNPs were further characterized by Raman spectroscopy, and electrical/electrochemical techniques. These electrodes were then applied for the electrochemical reduction of CO2, leading to the formation of compounds with one carbon atom (formic acid), two carbon atoms (ethenone), three carbon atoms (propanoic acid) and four carbon atoms (butanol and butanoic acid). Fil: Gomez, Federico Jose Vicente. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto de Biología Agrícola de Mendoza. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias. Instituto de Biología Agrícola de Mendoza; Argentina Fil: Chumanov, George. Clemson University; Estados Unidos Fil: Silva, María Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto de Biología Agrícola de Mendoza. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias. Instituto de Biología Agrícola de Mendoza; Argentina. Clemson University; Estados Unidos Fil: Garcia, Carlos D.. Clemson University; Estados Unidos

The properties of phosphonium polyelectrolytes (PELs) were evaluated in an effort to assess the influence of both side chain and main chain composition. The influence of side chain was examined by comparing properties of a series of PELs having hydrophobic octyloxy side chains to those of structural analogues lacking the side chains. The influence exerted by backbone flexibility/length of spacer between charges was revealed by comparing properties of two series of polymers with a variable number of methylene units between phosphonium charge‐bearing sites. Side chain composition and spacing between phosphonium units lead to noteworthy influence on thermal stability, glass transition, and crystallinity. The molecular structure of PELs also correlates with trends in film morphology and critical surface energy of PEL dip‐cast films. Sensitivity of morphology to humidity or water in the casting solvent was observed. Supramolecular assembly of films via layer‐by‐layer deposition of PELs alternating with anionic polythiophene derivative layers was also undertaken. The linearity of film growth, amount of material deposited in each bilayer, polycation:polyanion ratio, and film roughness all show noteworthy trends that depend on both the presence/absence of side chains and on spacing between ionic centers. The relationship between side chain and spacer on bactericidal activity against Staphylococcus aureus and Escherichia coli was assessed. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 24–34

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.

Electrochemical paper-based analytical devices represent an innovative and versatile platform for fluid handling and analysis. Nevertheless, the intrinsic structure of the paper can impose limitations to both the selection of the electrode material and the method selected to attach the electrodes to the device, potentially affecting the analytical performance of the device. To address these limitations, we herein propose carbon tape as a simple and low cost alternative to develop ePADs. The proposed material (in the form of tape or tabs) was first characterized using a combination of contact angle analysis, resistivity, Raman spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. Upon this initial assessment, carbon tape was selected and modified with carbon nanotubes, to provide not only a better surface for proteins to adhere to, but also an enhanced electroactive surface. The analytical performance of the resulting device was assessed by integrating three enzymes that facilitate the oxidation of ethanol, glucose, and phenol, and by performing the detection of these analytes in beer samples. The resulting device, for which materials cost less than a dollar, represents a simple alternative material for ePADs, applied in this case to monitor three of the most important parameters during the production of beers. Fil: Gomez, Federico Jose Vicente. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto de Biología Agrícola de Mendoza. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias. Instituto de Biología Agrícola de Mendoza; Argentina Fil: Reed, Paige A.. Clemson University. Department of Chemistry; Estados Unidos Fil: Gonzalez Casamachin, Diego. Universidad Autónoma de Nuevo León; México Fil: Rivera de la Rosa, Javier. Universidad Autónoma de Nuevo León; México Fil: Chumanov, George. Clemson University. Department of Chemistry; Estados Unidos Fil: Silva, María Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto de Biología Agrícola de Mendoza. Universidad Nacional de Cuyo. Facultad de Ciencias Agrarias. Instituto de Biología Agrícola de Mendoza; Argentina Fil: Garcia, Carlos D.. Clemson University. Department of Chemistry; Estados Unidos

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.

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 .

Carbon nanofibers of 1–2 nm height and micrometer length were synthesized via a hydrothermal conversion of cellulose nanocrystals at 240 °C. The fibers were characterized by atomic force microscopy, transmission electron microscopy, powder X-ray diffraction and Raman spectroscopy. In the hypothesized mechanism, the self-assembly of cellulose nanocrystals prior to their carbonisation provides a template for the nanofiber formation.

A cation exchange reaction of wide band gap crystalline ZnS with CuCl2 and SnCl4 in triethylene glycol was developed to synthesize nonstoichiometric Cu2ZnSnS4 with crystallite size more than 100 nm. The materials were characterized by powder X-ray diffraction, electron microscopy, Raman, and energy dispersive X-ray elemental mapping. The method allows the formation of Zn-rich phases and good control of the crystal size and shape. No narrow bandgap high conductive CuxS impurities were observed.

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.

PbI2-based photovoltaic devices having ITO/ZnO (or WO3) /PbI2/graphite (or without graphite) /carbon black structure were fabricated by spin coating at ambient conditions. The structures were characterized using AFM, PXRD, and UV–Vis spectroscopy. The best devices yielded 0.32% power conversion efficiency. The short circuit current decreased with increasing the thickness of the PbI2 film and without the graphite layer. The open circuit voltage decreased when replacing ZnO by WO3. Selecting better n-type and hole transporting materials as well as improving manufacturing methods will increase PCE of PbI2 based devices.

The conversion of CO

We have demonstrated the capability of a nanocomposite film made of a 2D array of Ag nanoparticles embedded into a poly(glycidyl methacrylate), PGMA, matrix to monitor the presence of organic vapors in the atmosphere. Specifically, changes in the extinction spectra of the submicron nanocomposite film are used to sense the vapors. The transformations of the spectra are fully reversible and reproducible upon multiple exposures. We associate this reversibility and reproducibility with the construction of the nanocomposite film where the cross-linked PGMA network is able to spatially restore its structure upon deswelling. The structure of the extinction spectrum of the film is governed by a collective surface plasmon mode excited in the Ag NPs array. It was found that spectral bands associated with normal and tangential components of the plasmon mode change their width and position when the nanocomposite is exposed to organic vapors. This is due to increasing the spacing between neighboring NPs and a decrease of the refractive index of the polymer caused by swelling of the PGMA matrix. Therefore, the level of spectral transformation is directly related to the level of polymer–solvent thermodynamic affinity where the higher affinity corresponds to the higher level of the swelling. Therefore, we expect that the nanocomposite films (when designed for a particular solvent) can be effectively used as a sensing element in a low-cost volatile organic compounds (VOC) sensor device operating in visual light.

Laser-driven hybridization of a collective surface plasmon mode of a monolayer of silver nanoparticles has been studied as a function of irradiation power density. Two collective surface plasmon modes were identified in the spectra, namely, T- and P-modes, associated with the induced particle dipoles parallel and perpendicular to the plane of the layer. The P-mode was in resonance with the laser irradiation wavelength (488 nm). The magnitude, spectral position, and bandwidth of the two modes depend significantly differently on the laser power density. The laser-driven changes of the T-mode were attributed to the thermal effects caused by laser heating of the sample. Meanwhile, the spectral behavior of the P-mode is governed by resonant excitation by an Ar laser.

Large single crystals of A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F were grown using a high-temperature (~600 °C) hydrothermal technique. Single crystal X-ray diffraction and powder X-ray diffraction were utilized to characterize the structures, which both possess MnO4F2 building blocks. The A2Mn2V2O7F2 series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb2Mn2V2O7F2: a=7.4389(17) A, b=11.574(3) A, c=10.914(2) A; Cs2Mn2V2O7F2: a=7.5615(15) A, b=11.745(2) A, c=11.127(2) A). The structure is composed of zigzag chains of edge-sharing MnO4F2 units running along the a-axis, and interconnected through V2O7 pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn2+ indicated that Cs2Mn2V2O7F2 is antiferromagnetic with a Neel temperature, TN=~3 K and a Weiss constant, θ, of −11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V–O vibrational modes in Cs2Mn2V2O7F2. Mn2(VO4)F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) A, b=6.8036(7) A, c=10.1408(13) A and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn2+. These interpenetrating chains are additionally connected through isolated VO4 tetrahedra to form the condensed structure.

New complex manganese vanadate materials were synthesized as high-quality single crystals in multi-millimeter lengths using a high-temperature, high-pressure hydrothermal method. One compound, Mn5(VO4)2(OH)4, was grown from Mn2O3 and V2O5 in 3 M CsOH at 580 °C and 1.5 kbar. Changing the mineralizer to 1 M CsOH/3MCsCl leads to the formation of another product, Mn6O(VO4)2(OH). Both compounds were structurally characterized by single-crystal X-ray diffraction (Mn5(VO4)2(OH)4: C2/m, Z = 2, a = 9.6568(9) Å, b = 9.5627(9) Å, c = 5.4139(6) Å, β = 98.529(8)°; Mn6O(VO4)2(OH): P21/m, Z = 2, a = 8.9363(12) Å, b = 6.4678(8) Å, c = 10.4478(13) Å, β = 99.798(3)°), revealing interesting low-dimensional transition-metal features. Mn5(VO4)2(OH)4 possesses complex honeycomb-type Mn-O layers, built from edge-sharing [MnO6] octahedra in the bc plane, with bridging vanadate groups connecting these layers along the a-axis. Mn6O(VO4)2(OH) presents a more complicated structure with both octahedral [MnO6] and trigonal bipyramidal [MnO5] units. A different pattern of planar honeycomb sheets are formed by edge-shared [MnO6] octahedra, and these sublattices are connected through edge-shared dimers of [MnO5] trigonal bipyramids to form corrugated sheets. Vanadate groups again condense the sheets into a three-dimensional framework. Infrared and Raman spectroscopies indicated the presence of OH groups and displayed characteristic Raman scattering due to vanadate groups. Temperature-dependent magnetic studies indicated Curie-Weiss behavior above 100 K with significant anti-ferromagnetic coupling for both compounds, with further complex magnetic behavior at lower temperatures. The data indicate canted anti-ferromagnetic order below 57 K in Mn5(VO4)2(OH)4 and below 45 K in Mn6O(VO4)2(OH). Members of another class of compounds, K2M3(VO4)2(OH)2 (M = Mn, Co), also containing a honeycomb-type sublattice, were also synthesized to allow a comparison of the structural features across all three structure types and to demonstrate extension to other transition metals.

A series of transition metal vanadate crystals were prepared using a high temperature (580 °C) hydrothermal method. The compounds all had the general formula A 2 AEM (VO 4 ) 2 ( A =K, Na, Li; AE =Ba, Sr; M =Co, Fe, Mn). They are all variations of the glaserite structural type and range in symmetry from P- 3 m 1 to P -3 to P 2 1 / c . Most of the derivatives contain a planar three-fold rotation operation, making them possible spin frustration candidates. Single crystal structural analyses were performed on many of the derivatives to obtain a detailed understanding of the distortions of the tetrahedral building blocks that accommodate the symmetry distortions. A hydrothermal growth method was developed to grow high quality single crystals of sizes up to 2–3 mm/edge. This method can be generalized for large crystal growth to enable magnetic and neutron diffraction studies that require relatively large single crystals.

A one-step method for synthesizing high concentrations of 40–400 nm silver nanoparticles coated with an ultra-thin silica shell is described. The shell thickness can be further increased via post-synthetic precipitation of sodium silicate. The nanoparticles exhibit remarkable stability and can be concentrated to as much as 50% by weight in water and some organic solvents. It was also demonstrated that silica species catalyze the seeding and growth of silver nanoparticles. The herein described particles were used to develop simple surface-enhanced Raman spectroscopy substrates and chemiresistors.

Pure 2H CuFeO2 nanoplates with a thickness of about 100 nm were synthesized at temperatures as low as 100 °C from CuI and FeCl3·6H2O. Systematic studies revealed that the formation of 2H CuFeO2 was affected by reactant concentrations, basicity, temperature and the reaction time. The material was characterized by powder X-ray diffraction, electron microscopy, Raman and absorption spectroscopy. 2H CuFeO2 has a band gap of 1.33 eV, high absorption coefficient of 3.8 × 104 cm−1 at 700 nm and is highly photostable. When incorporated into an indium tin oxide/ZnO/2H CuFeO2/graphite/carbon black structure an open circuit photovoltage of 0.29 V was observed. The material appears promising for solar applications.

In this paper we report on changes in the extinction spectra of a nanocomposite consisting of Ag nanoparticles arranged in 2D array and embedded into poly(glycidyl methacrylate) host matrix. Two collective surface plasmon modes denoted as P and T were identified in the spectrum. They associated with electric dipoles perpendicular and parallel to the plane of the array respectively. It was found experimentally that intensity and bandwidth of corresponding bands decrease when the nanocomposite is exposed to chloroform vapor. At the same time, both plasmon bands shift toward shorter wavelength. Those dependences can be explained by weakening of the electrodynamic coupling between LSPR in neighboring nanoparticles due to the increase of the distance between particles caused by swelling of the polymer matrix. The spectral changes are fully reversible. It was found that sensitivity of the nanocomposite sensor to chloroform vapor is 0.02 nm/ppm with the response time $t-25\ \text{s}$ .

Silver nanoparticles self-assembled on poly(4-vinylpyridine) modified surfaces were spin-coated with poly(methyl methacrylate), poly(butyl methacrylate) and polystyrene from anisole and toluene solutions. The polymers filled the space between the particles thereby providing stabilization of the assemblies against particle aggregation when dried or chemically modified. The polymers did not coat the top surface of the nanoparticles offering the chemical accessibility to the metal surface. This was confirmed by converting the stabilized nanoparticles into silver sulfide and gold clusters. Etching the nanoparticles resulted in crater-like polymeric structures with the cavities extending down to the underlying substrate. Electrochemical reduction of silver inside the craters was performed. The approach can be extended to other nanoparticle assemblies and polymers.

A new series of transition metal vanadates, namely, Ba2M(VO4)2(OH) (M = V(3+), Mn(3+), and Fe(3+)), was synthesized as large single crystals hydrothermally in 5 M NaOH solution at 580 °C and 1 kbar. This new series of compounds is structurally reminiscent of the brackebuschite mineral type. The structure of Ba2V(VO4)2(OH) is monoclinic in space group P21/m, a = 7.8783(2) Å, b = 6.1369(1) Å, c = 9.1836(2) Å, β = 113.07(3)°, V = 408.51(2) Å(3). The other structures are similar and consist of one-dimensional trans edge-shared distorted octahedral chains running along the b-axis. The vanadate groups bridge across edges of their tetrahedra. Structural analysis of the Ba2Mn(VO4)2(OH) analogue yielded a new understanding of the Jahn-Teller effect in this structure type. Raman and infrared spectra were investigated to observe the fundamental vanadate and hydroxide vibrational modes. Single-crystal temperature-dependent magnetic studies on Ba2V(VO4)2(OH) reveal a broad feature over a wide temperature range with maximum at ∼100 K indicating that an energy gap could exist between the antiferromagnetic singlet ground state and excited triplet states, making it potentially of interest for quantum magnetism studies.

A series of seven cationic polymers have been prepared wherein the length of spacer between charge-bearing sites has been varied. Thermal stability of the polymers was characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The length of spacer has obvious effect on thermal stability as well as on the extent of crystallinity as revealed by X-ray powder diffraction. The cationic polymers were tested for their ability to form supramolecularly-assembled films with an anionic polythiophene derivative by a layer-by-layer (LbL) deposition process. Film growth was followed by spectroscopic techniques and surface morphologies were examined by atomic force microscopy (AFM). Interesting dependence of film morphology and composition was observed depending on whether an even- or odd-number of methylene spacers was present between charge-bearing sites.

Despite noteworthy progress in the fabrication of large-area graphene sheetlike nanomaterials, the vapor-based processing still requires sophisticated equipment and a multistage handling of the material. An alternative approach to manufacturing functional graphene-based films includes the employment of graphene oxide (GO) micrometer-scale sheets as precursors. However, search for a scalable manufacturing technique for the production of high-quality GO nanoscale films with high uniformity and high electrical conductivity is still continuing. Here we show that conventional dip-coating technique can offer fabrication of high quality mono- and bilayered films made of GO sheets. The method is based on our recent discovery that encapsulating individual GO sheets in a nanometer thick molecular brush copolymer layer allows for the nearly perfect formation of the GO layers via dip coating from water. By thermal reduction the bilayers (cemented by a carbon-forming polymer linker) are converted into highly conductive and transparent reduced GO films with a high conductivity up to 104 S/cm and optical transparency on the level of 90%. The value is the highest electrical conductivity reported for thermally reduced nanoscale GO films and is close to the conductivity of indium tin oxide currently in use for transparent electronic devices, thus making these layers intriguing candidates for replacement of ITO films.

Two terbium germanates have been synthesized via high-temperature and high-pressure hydrothermal synthesis with 20 M KOH as a mineralizer using Tb

Three new barium manganese vanadates, all containing hexagonal barium chloride layers interpenetrated by [V2O7]4– groups, were synthesized using a high-temperature (580 °C) hydrothermal method. Two of the compounds were prepared from a mixed BaCl2/Ba(OH)2 mineralizer, and the third compound was prepared from BaCl2 mineralizer. An interesting structural similarity exists between two of the compounds, Ba2Mn(V2O7)(OH)Cl and Ba4Mn2(V2O7)(VO4)2O(OH)Cl. These two compounds crystallize in the orthorhombic space group Pnma, Z = 4, and are structurally related by a nearly doubled a axis. The first structure, Ba2Mn(V2O7)(OH)Cl (I) (a = 15.097(3) A, b = 6.1087(12) A, c = 9.5599(19) A), consists of octahedral manganese(II) edge-sharing chains linked by pyrovanadate [V2O7] groups, generating a three-dimensional structure. Compound II, Ba4Mn2(V2O7)(VO4)2O(OH)Cl (a = 29.0814(11) A, b = 6.2089(2) A, c = 9.5219(4) A), is composed of manganese(III) edge-sharing chains that are coordinated to one another through pyrovanadat...

We describe a simple technique to alter the shape of silver nanoparticles (AgNPs) by rolling a glass tube over them to mechanically compress them. The resulting shape change in turn induces a red-shift in the localized surface plasmon resonance (LSPR) scattering spectrum and exposes new surface area. The flattened particles were characterized by optical and electron microscopy, single nanoparticle scattering spectroscopy, and surface enhanced Raman spectroscopy (SERS). AFM and SEM images show that the AgNPs deform into discs; increasing the applied load from 0 to 100 N increases the AgNP diameter and decreases the height. This deformation caused a dramatic red shift in the nanoparticle scattering spectrum and also generated new surface area to which thiolated molecules could attach as evident from SERS measurements. The simple technique employed here requires no lithographic templates and has potential for rapid, reproducible, inexpensive and scalable tuning of nanoparticle shape, surface area, and resonance while preserving particle volume.

We established that metal–dielectric nanostructures (consisting of three stacked monolayers of silver nanoparticles incorporated into polymer cross-linked film) can demonstrate three different surface plasmon collective modes. The modes were detected when the extinction spectra of the nanostructures were studied as a function of the incident angle and polarization of the incident light. Two previously known surface plasmon collective modes, namely T and P, associated with particle dipoles parallel and perpendicular to plane of the layer were identified for the polymer films containing one, two, and three monolayers of the particles. The extinction bands of T and P modes exhibited different intensity and frequency dependences on the angle of incidence. More pronounced angular dependences for P mode band indicated the stronger coupling of dipoles for P mode than for T one. A new N mode was observed for the structures consisting of three nanoparticle layers. This mode originated from surface plasmon coupling between adjacent layers. The additional mode significantly increases amount of information that can be obtained from optical response of the nanostructures.

A new optical sensor based on the localized surface plasmon resonance (LSPR) in 2D arrays of silver nanoparticles (AgNPs) combined with a differential optical measurement method is developed. LSPR substrates comprised of self-assembled, 2D arrays of AgNPs exhibit coherent plasmon coupling manifested as a sharp peak in the blue spectral region. A bottom-up approach was used to fabricate reproducible and cost-effective substrates with a figure of merit (FOM) of ~24. The LSPR shift was determined by measuring the difference between light extinction at two wavelengths selected on each side of the sharp peak. The sharpness of the coherent plasmon resonance together with the differential measurement method enabled a record sensing resolution in bulk for a LSPR sensor of ~4.8E-6 RIU.

Silver nanoparticles have been modified with self-assembled monolayers of hydroxyl-terminated long chain thiols and encapsulated with a silica shell. The resulting core–shell nanoparticles were used as optical labels for cell analysis using flow cytometry and microscopy. The excitation of plasmon resonances in nanoparticles results in strong depolarized scattering of visible light, permitting detection at the single nanoparticle level. The nanoparticles were modified with neutravidin via epoxide–azide coupling chemistry, to which biotinylated antibodies targeting cell surface receptors were bound. The nanoparticle labels exhibited long-term stability in solutions with high salt concentrations without aggregation or silver etching. Labeled cells exhibited two orders of magnitude enhancement of the scattering intensity compared with unlabeled cells.

New complex manganese vanadate materials were synthesized as high-quality single crystals in multi-millimeter lengths using a high-temperature, high-pressure hydrothermal method. One compound, Mn5(VO4)2(OH)4, was grown from Mn2O3 and V2O5 in 3 M CsOH at 580 °C and 1.5 kbar. Changing the mineralizer to 1 M CsOH/3MCsCl leads to the formation of another product, Mn6O(VO4)2(OH). Both compounds were structurally characterized by single-crystal X-ray diffraction (Mn5(VO4)2(OH)4: C2/m, Z = 2, a = 9.6568(9) A, b = 9.5627(9) A, c = 5.4139(6) A, β = 98.529(8)°; Mn6O(VO4)2(OH): P21/m, Z = 2, a = 8.9363(12) A, b = 6.4678(8) A, c = 10.4478(13) A, β = 99.798(3)°), revealing interesting low-dimensional transition-metal features. Mn5(VO4)2(OH)4 possesses complex honeycomb-type Mn–O layers, built from edge-sharing [MnO6] octahedra in the bc plane, with bridging vanadate groups connecting these layers along the a-axis. Mn6O(VO4)2(OH) presents a more complicated structure with both octahedral [MnO6] and trigonal bipyramidal...

High quality single crystals with sizes up to 2—3 mm/edge of the transition metal vanadates (Va—g) are hydrothermally prepared and their structures are determined by single crystal XRD.

Depolarized scattering spectra from individual silver nanoparticles of different shapes and sizes were measured as a function of the incident polarization angle. The spectra were correlated to the nanoparticles’ shape, size, and orientation as determined by scanning electron microscopy. The intensity of depolarized scattered light from nonspherical silver nanoparticles strongly depends upon particle shape and orientation relative to the polarization vector. The intensity of depolarized scattered light also increases with the aspect ratio of the nanoparticles. The depolarized light scattering originated from the interference of the plasmon modes corresponding to the electron oscillations along different axes of the NPs.

Imaging of micro- and nanofluidics is a challenge since the size of the channels is so small that the installment of additional optical and mechanical switches is very difficult. The size of the device and associated increase in viscous dissipation constitute another constraint. In response to these limitations, this work proposes and demonstrates the manipulation of light by adding a functional lens to control the light on demand. In the present work, this lens is realized by filling a hollow fiber with a colloid of superparamagnetic Fe3O4 nanoparticles. When the propagation of light is perpendicular to the magnetic field, this lens stretches the circular beam into a ribbon yielding a larger visible area. Potentially, one can apply a rotating magnetic field thus illuminating a larger spot size or creating other beam geometries. Such composite fibers might also be of value for Faraday isolation and other magneto-optic effects in optical fibers. Published by Elsevier B.V.

Binary polymer nanoparticles were synthesized by the reprecipitation of poly(4-vinylpyridine) in the presence of poly(diallyldimethylammonium chloride) and further used to make polymer-coated Ag nanoparticles. Polymer shells around Ag nanoparticles were formed by two methods: the reduction of Ag(2)O in the presence of the polymer nanoparticles and by mixing the polymer nanoparticles with already-made Ag nanoparticles. The resulting nanoparticles were coated with layers of the two polymers with the hydrophilic polymer on the outside providing their stability in water. The exposure of the polymer-coated Ag nanoparticles to unmodified Ag nanoparticles resulted in spontaneous self-assembly due to the electrostatic attraction. The polymer-coated nanoparticles and the nanoparticle assemblies were characterized by UV-vis, surface-enhanced Raman scattering spectroscopy, and transmission electron microscopy.