Douglas Hagrman

Organic-inorganic hybrid materials: From 'simple' coordination polymers to organodiamine-templated molybdenum oxides

A blueprint for the design of oxide materials is provided by nature. By borrowing from natures ability to influence inorganic microstructures in biomineralization processes and in the hydrothermal synthesis of complex minerals, a new class of materials in which organic components exert a role in controlling inorganic microstructure is evolving. By employing members of the ever-expanding class of polymeric coordination complex cations, novel molybdenum oxide substructures, such as the one shown, may be prepared.

Solid-State Coordination Chemistry: The Self-Assembly of Microporous Organic–Inorganic Hybrid Frameworks Constructed from Tetrapyridylporphyrin and Bimetallic Oxide Chains or Oxide Clusters

The hydrothermal reactions of MoO(3), tetrapyridylporphyrin (tpypor), water, and the appropriate M(II) precursor yield the first examples of three-dimensional framework materials constructed from metal oxide and porphyrin subunits. The picture shows a section of [{Fe(tpypor)}(3)Fe(Mo(6)O(19))(2)] small middle dotx H(2)O with the [Fe(8)(tpypor)(6)](8+) building block of the cationic framework and the entrained {Mo(6)O(19)}(2-) cluster.

Organisch-anorganische Hybridmaterialien: von „einfachen” Koordinationspolymeren zu Molybdänoxiden mit Organodiamin-Templaten

Eine Blaupause fur das Design von Oxidmaterialien kann uns die Natur liefern, da sie bei Biomineralisationsprozessen und bei der Hydrothermalsynthese komplexer Mineralien anorganische Mikrostrukturen beeinflussen kann. Eine Anleihe bei dieser Fahigkeit fuhrt zu einer ganz neuen Klasse von Materialien, bei denen organische Komponenten eine Rolle bei der Kontrolle uber die anorganischen Mikrostrukturen spielen. Der Einsatz von Verbindungen aus der bestandig wachsenden Klasse polymerer Komplexkationen ermoglicht die Herstellung von Molybdanoxiden mit neuartigen Substrukturen (siehe das im Bild gezeigte Beispiel).

Organic/inorganic composite materials: the roles of organoamine ligands in the design of inorganic solids

Abstract The influence of organic components on the microstructure of inorganic solids has been extensively documented in recent years and has been shown to provide an efficacious method for the design of new materials. The synergism between the various chemical constituents at the organic/inorganic interface may result in imprinting of structural information from the organic molecules onto the inorganic framework. In this paper, the structural consequences of introducing organic components into several families of materials, including oxometalphosphates, transition metal oxides and transition metal halides and pseudohalides are briefly reviewed.

Polyoxomolybdate clusters and copper–organonitrogen complexes as building blocks for the construction of composite solids

Abstract The influences of ligand coordination modes on the oxide microstructures in the copper molybdate system were investigated. Rigid bridging ligands such as 4,4′-bypyridine (4,4′-bpy) and 2,4,6-tripyridyltriazine (tptz) afford polymeric cationic substructures with Cu(I) which provide scaffoldings for the entrainment and modification of the molybdenum oxide microstructure. These structural influences are manifested in [{Cu(4,4′-bpy)} 2 Mo 2 O 7 ] ( MOXI-45 ) and [{Cu(tptz)} 2 Mo 6 O 19 ] ( MOXI-46 ). In contrast, ligands such as pyridine (py) which do not effect the construction of polymeric substructures provide molecular building blocks which combine with the molybdenum oxide motifs in a less predictable fashion. Thus, [{Cu(py)} 4 Mo 8 O 26 ] ( MOXI-47 ) is constructed from octamolybdate clusters linked by {Cu(py)} +1 fragments into a virtual two-dimensional network. The interplay of ligand geometry and bonding mode and of metal coordination preferences plays an important role in the structure of [{Cu 2 (tpypz)(H 2 O) 2 }Mo 8 O 26 ] ( MOXI-44 ), the unique example of a Cu(II)-containing material, with the binucleating tetrapyridylpyrazine ligand (tpypz) providing the organic building unit. The overall structure reflects the binucleating role of the ligand and the distorted octahedral geometry of the Cu(II) centers. The importance of hydrothermal techniques in effecting the syntheses of such composite materials is also discussed.

The Structural Role of Metal-Organonitrogen Subunits in the Molecular Manipulation of Molybdenum Oxides

Abstract Although solid state metal oxides are of both fundamental and practical interest, the designed synthesis of such materials remains an elusive goal. However, valuable synthetic guidelines may be derived from a consideration of the plethora of Natures remarkable materials which contain composites of molecules or microstructures in which inorganic components coexist with organic components. The presence of organic subunits can profoundly influence the crystallization of the inorganic microstructure, offering a powerful tool for the design of novel materials. In the specific case of molybdenum oxide phases, metal-organoamine molecules, fragments, an even polymeric coordination complex cations may be exploited in the self-assembly of complex hierarchical materials.

Effect of hemoglobin concentration variation on the accuracy and precision of glucose analysis using tissue modulated, noninvasive, in vivo Raman spectroscopy of human blood: a small clinical study

Tissue modulated Raman spectroscopy was used noninvasively to measure blood glucose concentration in people with type I and type II diabetes with HemoCue fingerstick measurements being used as reference. Including all of the 49 measurements, a Clarke error grid analysis of the noninvasive measurements showed that 72% were A range, i.e., clinically accurate, 20% were B range, i.e., clinically benign, with the remaining 8% of measurements being essentially erroneous, i.e., C, D, or E range. Rejection of 11 outliers gave a correlation coefficient of 0.80, a standard deviation of 22 mg/dL with p<0.0001 for N=38 and places all but one of the measurements in the A and B ranges. The distribution of deviations of the noninvasive glucose measurements from the fingerstick glucose measurements is consistent with the suggestion that there are at least two systematic components in addition to the random noise associated with shot noise, charge coupled device spiking, and human factors. One component is consistent with the known variation of fingerstick glucose concentration measurements from laboratory reference measurements made using plasma or whole blood. A weak but significant correlation between the deviations of noninvasive measurements from fingerstick glucose measurements and the test subjects hemoglobin concentration was also observed.

Progress in the noninvasive in-vivo tissue-modulated Raman spectroscopy of human blood

We have recently presented the first Raman spectra of in vivo human blood. A brief review of how to obtain such spectra and normalize them to the appropriate blood volume is given showing how to produce spectra that can be used for noninvasive quantitative analysis of blood in vivo. New clinical data from individuals and groups completely reproduce and extend all the earlier results. These new data reveal how certain small differences between individuals result in some variability in their noninvasive quantitation. We show the origin of this variability and how to obtain quantitative corrections based entirely on the individual measurement and tabulated data.

Organic–inorganic composite oxide phases: one-dimensional molybdenum oxide chains entrained within a three-dimensional coordination complex cationic framework in [{Cu2(triazolate)2(H2O)2}Mo4O13]

The hydrothermal reaction of MoO3, CuSO4·5H2O, 1,2,4-triazole and H2O produces a 50% yield of [{Cu2-(triazolate)2(H2O)2}Mo4O13], a material constructed from {Mo4O13}n2n– chains entrained within the three dimensional framework provided by the {Cu2(triazolate)2(H2O)2}n2n+ polymeric complex.

A two-dimensional network constructed from hexamolybdate, octamolybdate and [Cu3(4,7-phen)3]3+ clusters: [{Cu3(4,7-phen)3}2{Mo14O45}]

The hydrothermal reaction of Cu(SO4)·H2O, MoO3, 4,7-phenanthroline and water yields [{Cu3(4,7-phen)3}2{Mo14O45}], a material exhibiting a two-dimensional network constructed from (Mo6O19)2– and (Mo8O26)4– clusters linked through planar cyclic {Cu3(4,7-phen)33}+ clusters.