Two Homologous Intermetallic Phases In The Na–Au–Zn System With Sodium Bound In Unusual Paired Sites Within 1d Tunnels, Saroj L. Samal, Qisheng Lin, John D. Corbett
The Na–Au–Zn system contains the two intermetallic phases Na0.97(4)Au2Zn4 (I) and Na0.72(4)Au2Zn2 (II) that are commensurately and incommensurately modulated derivatives of K0.37Cd2, respectively. Compound I crystallizes in tetragonal space group P4/mbm (No. 127), a = 7.986(1) Å, c = 7.971(1) Å, Z = 4, as a 1 × 1 × 3 superstructure derivative of K0.37Cd2 (I4/mcm). Compound II is a weakly incommensurate derivative of K0.37Cd2 with a modulation vector q = 0.189(1) along c. Its structure was solved in superspace group P4/mbm(00g)00ss, a = 7 ...
Superconducting Properties Of Rh 9 In 4 S 4 Single Crystals, 2017 Iowa State University
Superconducting Properties Of Rh 9 In 4 S 4 Single Crystals, Udhara S. Kaluarachchi, Qisheng Lin, Weiwei Xie, Valentin Taufour, S. L. Bud’Ko, Gordon J. Miller, Paul C. Canfield
The synthesis and crystallographic, thermodynamic, and transport properties of single crystalline Rh9In4S4 were studied. The resistivity, magnetization, and specific heat measurements all clearly indicate bulk superconductivity with a critical temperature, Tc∼2.25 K. The Sommerfeld coefficient γ and the Debye temperature (ΘD) were found to be 34 mJ mol−1 K−2 and 217 K, respectively. The observed specific heat jump, ΔC/γTc=1.66, is larger than the expected BCS weak coupling value of 1.43. Ginzburg-Landau (GL) ratio of the low-temperature GL-penetration depth, λGL≈5750 Å, to the GL-coherence length, ξGL≈94 Å, is large: κ ∼60 ...
Synthesis, Structure, And Bonding Of Sc4mgxcu15-Xga~7.5 (X = 0, 0.5): Two Incommensurately Modulated Scandium Substitution Derivatives Of Cubic Mg2cu6ga5, Qisheng Lin, Sven Lidin, John D. Corbett
The substitution of scandium for magnesium in Mg2Cu6Ga5 (Mg2Zn11-type) yields an irrational superstructure phase that includes the refined compositions, Sc4Mg0.50(2)Cu14.50(2)Ga7.61(2) and Sc4Cu14.76(2)Ga7.51(2). These crystallize in Cmmm, a = ∼8.31 Å, b = ∼21.72 Å, c = ∼8.30 Å. The structures feature Sc2 dimers, Cu6 octahedra, a 3D CuGa (Cu12Ga2) framework, and arachno gallium-centered Cu4Ga6 icosahedra that are condensed into zigzag chains. The arrangement of these building blocks exhibits a topologic relationship to Mg2Cu6Ga5. Further studies reveal that the quaternary compound exhibits incommensurate modulations along a, with q ...
M3(Au,Ge)19 And M3.25(Au,Ge)18 (M = Ca, Yb): Distinctive Phase Separations Driven By Configurational Disorder In Cubic Ycd6-Type Derivatives, Qisheng Lin, John D. Corbett
Exploratory syntheses in the M−Au−Ge (M = Ca, Yb) systems have led to the discovery of two cleanly separated non-stoichiometric phases M3Au∼14.4Ge∼4.6 (I) and M3.25Au∼12.7Ge∼5.3 (II). Single crystal X-ray studies reveal that both (space group Im3̅) feature body-centered-cubic packing of five-shell multiply endohedral clusters that resemble those in the parent YCd6 (= Y3Cd18) and are akin to approximate phases in other quasicrystal systems. However, differences resulting from various disorders in these are distinctive. The innermost cluster in the M3Au∼14.4Ge∼4.6 phase (I) remains a disordered tetrahedron, as ...
Li14.7mg36.8cu21.5ga66: An Intermetallic Representative Of A Type Iv Clathrate, 2017 The Ames Laboratory
Li14.7mg36.8cu21.5ga66: An Intermetallic Representative Of A Type Iv Clathrate, Qisheng Lin, John D. Corbett
Synthetic explorations in the quaternary Li−Mg−Cu−Ga system yield the novel intermetallic Li14.7(8)Mg36.8(13)Cu21.5(5)Ga66 [P6̅m2, Z = 1, a = 14.0803(4) Å, c = 13.6252 (8) Å] from within a limited composition range. This contains a unique three-dimensional anionic framework consisting of distinct interbonded Ga12 icosahedra, dimerized Li@(Cu,Mg)10Ga6 icosioctahedra, and 15-vertex Li@(Cu,Mg)9Ga6 and Li@Cu3Ga12 polyhedra. These polyhedral clusters are hosted by M20 (512), M24 (51262), and M26 (51263) (M = Li/Mg) cages, respectively. The geometries and arrangements of these cages follow those ...
Multiple Nonstoichiometric Phases With Discrete Composition Ranges In The Caau5-Caau4bi-Biau2 System. A Case Study Of The Chemistry Of Spinodal Decomposition, Qisheng Lin, John D. Corbett
Synthetic explorations in the CaAu5−CaAu4Bi−BiAu2 system at 400 °C reveal five separate solid solution regions that show three distinct substitution patterns in the CaAu5 parent: (I) CaAu4(Au1−mBim) with 0 ≤ m ≤ 0.15(1), (II) 0.33(1) ≤ m ≤ 0.64(1), (III) 0.85(4) ≤ m ≤ 0.90(2); (IV) (Ca1−rAur)Au4(Bi1−sAus) with 0 ≤ r ≤ 0.39(1) and 0 ≤ s ≤ 0.12(2); (V) (Ca1−p−qAupBiq)Au4Bi with 0.09(2) ≤ p ≤ 0.13(1) and 0.31(2) ≤ q ≤ 0.72(4). Single crystal X-ray studies establish that all of ...
Formation Of Nets Of Corner-Shared Bicapped Gold Squares In Srau3ge: How A Baal4-Type Derivative Reconciles Fewer Valence Electrons And The Origin Of Its Uniaxial Negative Thermal Expansion, 2017 The Ames Laboratory
Formation Of Nets Of Corner-Shared Bicapped Gold Squares In Srau3ge: How A Baal4-Type Derivative Reconciles Fewer Valence Electrons And The Origin Of Its Uniaxial Negative Thermal Expansion, Qisheng Lin, John D. Corbett
SrAu3Ge was synthesized by direct fusion of the mixed elements at high temperature followed by annealing treatments, and its structure was determined by single crystal X-ray diffraction means in space group (Pearson symbol: tP10) P4/nmm, a = 6.264(1) Å, c = 5.5082(9) Å, Z = 2 at room temperature. The structure of SrAu3Ge, a reapportioned √2 × √2 × 1 superstructure of CeMg2Si2(P4/mmm), exhibits checkerboard nets of corner-shared bicapped Au squares (or corner-shared Au(Au4/2)Ge octahedra), in which the apical Au–Ge pairs in adjoining nets are strongly interbonded in the c direction. This motif contrasts ...
Centric And Non-Centric Ca3au~7.5ge~3.5: Electron-Poor Derivatives Of La3al11. Syntheses, Structures, And Bonding Analyses, Qisheng Lin, John D. Corbett
Two La3Al11 type derivatives have been discovered in the Ca−Au−Ge system and structurally characterized by single-crystal X-ray diffraction. Compositions Ca3Au7.16(6)Ge3.84(6) (1) and Ca3Au7.43(9)Ge3.57(9) (2) lie within a non-centric Imm2 phase region with a ≈ 4.40 Å, b ≈ 13.06 Å, c ≈ 9.60 Å. The Au-richer and electron-poorer Ca3Au7.50(1)Ge3.50(1) (3) and Ca3Au8.01(1)Ge2.99(1)(4) occur within a centric Pnnm phase region with a ≈ 9.50 Å, b ≈ 13.20 Å, c ≈ 4.43 Å. Both phases contain complex ...
Exploratory Syntheses And Structures Of Srau4.3in1.7 And Caag3.5in1.9: Electron-Poor Intermetallics With Diversified Polyanionic Frameworks That Are Related To Ycd6-Type Quasicrystal, 2017 The Ames Laboratory
Exploratory Syntheses And Structures Of Srau4.3in1.7 And Caag3.5in1.9: Electron-Poor Intermetallics With Diversified Polyanionic Frameworks That Are Related To Ycd6-Type Quasicrystal, Qisheng Lin, John D. Corbett
The phase regions around quasicrystals and approximants (QC/ACs) are rich pools for electron-poor intermetallics with novel, complex structures, and bonding patterns. The present SrAu4.30(1)In1.70(1) (1) and CaAg3.54(1)In1.88(1) (2) were synthesized through chemical tunings of the model CaAu4In2 (YCd6-Type) AC. Single crystal X-ray diffraction analyses reveals that crystal 1 has Pnma (CeCu6-type) symmetry, with a = 9.102(1) Å, b = 5.6379(9) Å, and c = 11.515(2) Å. The building block in 1 is a 19-vertex cluster Sr@Au9In4M6 (M = Au/In), which vividly mimics Ca@(Au,In ...
Gold Network Structures In Rhombohedral And Monoclinic Sr2au6(Au,T)3 (T= Zn, Ga). A Transition Via Relaxation, 2017 Iowa State University
Gold Network Structures In Rhombohedral And Monoclinic Sr2au6(Au,T)3 (T= Zn, Ga). A Transition Via Relaxation, Trinath Mishra, Qisheng Lin, John D. Corbett
Quantitative syntheses, structure determinations and interpretations, and band calculations are reported for the nonstoichiometric rhombohedral (R3̅c) and monoclinic (C2/c) Sr2Au6(Au3–xTx) (T = Zn, Ga) compounds. Several different compositions of the two Sr phases were similarly refined from single crystal X-ray diffraction data as R3̅c: a ≈ 8.43 Å, c ≈ 21.85 Å, Z = 6 and C2/c: a ≈ 14.70 Å, b ≈ 8.47 Å, c ≈ 8.70 Å, β ≈ 123.2°, Z = 4. The R3̅c Zn phase is stable in the composition region x ∼ 2.5–2 ...
Disorder–Order Structural Transformation In Electron-Poor Sr3au8sn3 Driven By Chemical Bonding Optimization, Qisheng Lin, Jordan Vetter, John D. Corbett
Sr3Au8Sn3 was synthesized through fusion of a stoichiometric amount of pure metals at 800 °C and annealing treatments at lower temperatures. Single-crystal X-ray diffraction analyses revealed that Sr3Au8Sn3 has a La3Al11-type Immm structure (a = 4.6767(8) Å, b = 9.646(2) Å, c = 14.170(2) Å, Z = 2) if annealed at 550 °C and above but a Ca3Au8Ge3-type structure (Pnnm, a = 9.6082(8) Å, b = 14.171(1) Å, c = 4.6719(4) Å, Z = 2) if annealed at 400 °C. The transition occurs at about 454 °C according to DTA data. Both structures feature columns of ...
Design Of Collagen-Mimetic Peptides, 2017 The Graduate Center, City University of New York
Design Of Collagen-Mimetic Peptides, Parminder Jeet Kaur
All Graduate Works by Year: Dissertations, Theses, and Capstone Projects
Collagen is the major component of the extracellular matrix and is involved in a wide range of cellular functions during tissue development and action. At the core of the diverse functions of this versatile protein is its remarkable ability to form supramolecular structures through self-assembly and/or through interactions with other biomolecules. One typical example of such supramolecular structure is the fibrils of collagen types I, II and III of the connective tissues. These fibrils have staggered arrangement of the laterally associated collagen triple helices – the structural unit of collagen – to form long, smooth fibrils with a characteristic 67 nm ...
Self-Immolative Phthalate Esters Sensitive To Hydrogen Peroxide And Light, 2017 Iowa State University
Self-Immolative Phthalate Esters Sensitive To Hydrogen Peroxide And Light, Kaitlyn M. Mahoney, Pratik P. Goswami, Aleem Ayed, Patrick Kolker, Brian Shannan, Emily A. Smith, Arthur Winter
Self-immolative aryl phthalate esters were conjugated with cleavable masking groups sensitive to light and hydrogen peroxide. The phthalate linker releases the fluorescent dye 7-hydroxycoumarin upon exposure to light or H2O2, respectively, leading to an increase in fluorescence. The light-sensitive aryl phthalate ester is demonstrated as a pro- fluorophore in cultured S2 cells
Energetic Effects Of Hole Transporting Materials On The Performance Of Organometal Halide Perovskite Photovoltaic Cells, So Min Park
Theses and Dissertations--Chemistry
Efficient, inexpensive, lightweight and flexible solar cells are desired to help meet the world’s growing energy needs. Organometal halide perovskite (OMHP) photovoltaic (PV) cells have shown dramatic increases in solar cell efficiencies increase over the last 5 years. OMHP PV cells have attracted significant attention due to their broad absorption spectra, high electron and hole mobility, and low production cost. The interface between hole transporting layer (HTL) and perovskite thin films have a significant influence on charge transfer and overall solar cell performance. 2,2’,7,7’-tetrakis(N,N-di-p-methoxyphenylamine)9,9’-spirobifluorene (Spiro-OMeTAD) is a small molecule largely ...
Superconductivity Versus Structural Phase Transition In The Closely Related Bi2rh3.5s2 And Bi2rh3s2, 2016 Iowa State University
Superconductivity Versus Structural Phase Transition In The Closely Related Bi2rh3.5s2 And Bi2rh3s2, Udhara S. Kaluarachchi, Weiwei Xie, Qisheng Lin, Valentin Taufour, Sergey L. Bud'ko, Gordon J. Miller, Paul C. Canfield
Single crystals of Bi2Rh3S2 and Bi2Rh3.5S2 were synthesized by solution growth, and the crystal structures and thermodynamic and transport properties of both compounds were studied. In the case ofBi2Rh3S2, a structural first-order transition at around 165 K is identified by single-crystal diffraction experiments, with clear signatures visible in resistivity, magnetization, and specific heat data. No superconducting transition for Bi2Rh3S2 was observed down to 0.5 K. In contrast, no structural phase transition at high temperature was observed for Bi2Rh3.5S2; however, bulk superconductivity with a critical temperature, Tc≈1.7 K, was observed. The Sommerfeld coefficient γ and the ...
Synthesis Of Metal-Containing Phosphines And Their Use In Coordination, Polymer, And Materials Chemistry, 2016 The University of Western Ontario
Synthesis Of Metal-Containing Phosphines And Their Use In Coordination, Polymer, And Materials Chemistry, Amir Rabiee Kenaree
Electronic Thesis and Dissertation Repository
This thesis describes the investigation of a novel strategy for the synthesis of metal-containing small molecules, polymers, and nanomaterials. In this context, a new family of air-stable, homo- and heterometallic primary, secondary, and tertiary phosphines were prepared via the radical-initiated hydrophosphination reaction of PH3 with vinylferrocene and/or vinylruthenocene. The full characterization of the phosphines confirmed their targeted structures and proved that the properties of the starting metallocenes are reflected in those of the resulting phosphines.
To study the coordination behavior of this family of phosphines, primary, secondary, and tertiary ethylferrocene phosphines were reacted with Group 6 metal carbonyl ...
Synthesis Of Metal-Containing Polymers And Stable Organic Radical-Containing Polymers And Their Use As Advanced Functional Materials, 2016 The University of Western Ontario
Synthesis Of Metal-Containing Polymers And Stable Organic Radical-Containing Polymers And Their Use As Advanced Functional Materials, Joseph A. Paquette
Electronic Thesis and Dissertation Repository
The work presented in this thesis details the synthesis and characterization of two different families of multifunctional polymers. The first family involved the incorporation of stable 6-oxoverdazyl radicals into polymer scaffolds. This was originally achieved by the polymerization of the radical precursors, phenyl- and isopropyl-6-oxotetrazanes, followed by post-polymerization oxidation to afford the phenyl- and isopropyl-6-oxoverdazyl polymers. A second methodology involved the direct polymerization of isopropyl-6-oxoverdazyl radicals using ring-opening metathesis polymerization (ROMP) to afford polymers with controlled molecular weights and narrow molecular weight distributions. The polymers were characterized by the close comparison of the physical and spectroscopic properties ...
Polyol Induced Partitioning Of Essential Oils In Aqueous Organic Solvent Mixtures, 2016 Seton Hall University
Polyol Induced Partitioning Of Essential Oils In Aqueous Organic Solvent Mixtures, Thomas Delmastro
Seton Hall University Dissertations and Theses (ETDs)
Polyol Induced Extraction (PIE) was developed and patented at Seton Hall University by Drs. John R. Sowa Jr., Wyatt R. Murphy, and Mithilesh Deshpande. It was originally discovered and implemented as a method to recycle and reuse waste acetonitrile during the production shortage in 2008. Through the use of PIE, a solvent mixture containing acetonitrile and water can be separated by employing a polyol mass separating agent, which induces a phase separation. The system is separated into its corresponding aqueous and organic phases, with the organic phase being a highly purified organic liquid. Based on the successful experimental results that ...
Design And Synthesis Of Novel Octacarboxy Porphyrinic Metal-Organic Frameworks, 2016 University of Nebraska - Lincoln
Design And Synthesis Of Novel Octacarboxy Porphyrinic Metal-Organic Frameworks, Jacob A. Johnson
Student Research Projects, Dissertations, and Theses - Chemistry Department
Metal-Organic Frameworks (MOFs) are a class of nanoporous crystalline materials constructed via the interconnection between metal-ions/inorganic clusters and organic ligands. Since the surface area, pore size and distribution, and chemical functionalities of MOFs are highly tunable via the judicious combinations of inorganic clusters and organic ligands, MOFs have attracted intensive interests for a variety of applications including gas adsorption and separation, catalysis, chemical sensing, and drug delivery among others. Porphyrin based ligands are of particular interest for building functional MOFs due to their unique photo-, electro-, and catalytic properties. In addition, the four-fold symmetry of porphyrin ligands offers an ...
Development Of An F-Element Separation Chemistry Using Solid Electrolytes, 2016 University of Tennessee, Knoxville
Development Of An F-Element Separation Chemistry Using Solid Electrolytes, Kristian Guy Myhre
The f‒elements (lanthanides and actinides) have numerous applications and are critically important to many industries, including the energy, security, and medical industries. One of the barriers to increased use and availability of the f‒elements is the difficulty in separating them from each other due to their similar chemistries. This is especially true of the trivalent f‒elements (lanthanides and minor actinides). The development of separation techniques that maximize the differences in the physicochemical properties of the f‒elements is therefore an important area of research. For these reasons, an effort was undertaken to explore the use of solid ...