Preparation and Characterization of Binder for Inorganic Composites Made from Amorphous Mineral Raw Material

The preparation and characterization of a composite binder made through a sol-gel route from an amorphous mineral raw material has been studied. The amorphous mineral raw material is alumino-silicate based but contains also alkaline earth and some transition metal oxides. A stable sol can be prepared by dissolving the raw materials in formic acid. The drying and heat treatment of the subsequent gel has been studied by thermogravimetry, nuclear magnetic resonance, infrared spectroscopy as well as X-ray diffraction studies. The different constituents of the raw material have shown to play a major role during the drying and heat treatment of the gels. The binding effect of the binder was evaluated to be good by studying paper-binder composites as well as wetting properties.     

The thermal decomposition of group iib metal halide complexes: Part II. N,N,N′,N′-tetramethylethylenediamine and 1,2-diphenylphosphinoethane complexes

The preparation and pyrolysis procedures for 1/1 complexes MX₂·L (where M = Group IIB metal, XCl, Br or I and LN,N,N′,N′-tetramethylethylene-diamine (TMED) or 1,2-diphenylphosphinoethane (DPE))is reported. The decomposition of the cadmium chloride and bromide TMED complexes afford intermediates of varying stability. From far infrared spectrophotometry we conclude that the chloride intermediate is a four coordinate polymeric complex. Differential scanning calorimetry has been used to determine selected latent heats of fusion.     

Emulsion copolymerization of tribromophenyl maleimide with styrene

Emulsion copolymerization of Tribromophenyl Maleimide (TBPMI) and styrene was conducted by semi-batch and batch processes. The effects of monomer composition and copolymerization method on copolymerization rate, molecular weight and molecular weight distribution, latex particle size and size distribution, glass transition temperature (T_g), thermal stability and mechanical properties were investigated. A kinetic study has shown that the rate of copolymerization in the batch process increased with increasing TBPMI content in the monomer feed. For the semi-batch polymerized samples, molecular weight decreased and molecular weight distribution increased with increasing TBPMI content in the monomer feed. For the batch polymerized samples, molecular weight also decreased but no obvious tendency was observed for the molecular weight distribution when TBPMI content increased. Compared with the batch copolymers, the semi-batch copolymers have a higher molecular weight at the same initial monomer mixture composition. Latex particle size decreased, while particle size distribution slightly increased with increasing TBPMI content in both semi-batch and batch latices. The semi-batch samples exhibit only a single T_g, the value of which increses linearly with increasing TBPMI content. For the batch copolymers, two T_gs were found, reflecting a mixture of styrene-rich and TBPMI-rich copolymer chains. TGA results indicate that the thermal stability of the semi-batch copolymers increased with increasing TBPMI concentration. Young's and flexural moduli increased, while tensile and flexural strengths decreased by increasing the TBPMI content for both the semi-batch and batch specimens. The semi-batch specimens have higher tensile and flexural strenghts than the batch ones.     

Mates toE=mc 2 and to the Heisenberg uncertainty relations

E=mc ² is found to be a special case ofE= ^±1cⁿ, where is any one of four susceptibilities, namely electric, magnetic, gravitational, and elastic. Letl be length,t time,t time dilation, andl a measure of Fitzgerald-Lorentz contraction. A particle is stated to be the manifestation of a collection of susceptibilities which arise when(l)/1=(t)/t. Then(E)/E=5 (t)/2t=±()/. Corresponding to susceptibility, special energy particles are postulated which exhibitSU(3) symmetry, Related to the susceptibilities are five new Heisenberg uncertainty relations. Three new conservation laws for particles are proposed.     

A study of the redox properties of MoOx/SiO2

A sample of MoOx/SiO2, in which all of the Mo cations are present as isolated mono-oxo molybdate moieties, was prepared and investigated to understand the redox chemistry of such molybdate species and their ability to exchange oxygen with O2 and H2O. Raman spectroscopy was used to monitor the exchange of 18O for 16O in the Mo=O bond of isolated molybdate species, whereas mass spectrometry was used to follow the isotopic composition of the gaseous species, i.e., O2 and H2O. Reduction in H2 at 920 K results in the loss of one O atom per Mo atom, and consistent with this, all of the Mo(VI) cations are reduced to Mo(IV) cations. Raman spectroscopy shows that virtually all Mo=O bonds of the original molybdate species are lost upon reduction. While reoxidation of Mo(IV) cations by O2 is quantitative, studies using 18O2 reveal that only a small part of the newly formed Mo=O bonds are 18O labeled, and that the balance are 16O labeled, indicating that O-atom exchange between the support, SiO2, and the supported MoOx species occurs during reoxidation. Rapid exchange of O atoms was observed upon exposure of both bare SiO2 and MoOx/SiO2 to H2(18)O at 920 K, and the presence of MoOx species was found to enhance the rate of exchange. By contrast, very slow exchange of O atoms was observed when the oxidized catalyst was exposed to 18O2 at 920 K. In situ observations of the catalyst during exposure to a mixture of H2 and 18O2 at 920 K showed that all of the Mo cations remained in the VI oxidation state and that O atom exchange occurred at a rate comparable to that observed upon exposure to H2(18)O. The results of this investigation suggest that reoxidation of Mo(IV) cations following H2 reduction involves the formation of a Mo-peroxide species and subsequent O atom migration from such a species to the SiO2 support. It is proposed that the steady-state oxidation of H2 also involves the formation of Mo-peroxide species by interaction of O2 with a small number of Mo(IV) centers. The Mo-peroxide species are then rapidly reduced by H2 to form H2O and a Mo=O bond. The rapid exchange of O atoms between the gas phase and the catalyst observed during steady-state oxidation of H2 is attributed to interactions of the product H2O with the catalyst, rather than to O atom migration originating from the Mo-peroxide species formed on the catalyst surface.     

Fragmentation and reactions of two isomeric O-alkyl S-(2-dialkylamino)ethyl methylphosphonothiolates studied by electrospray ionization/ion trap mass spectrometry

An initial investigation into the electrospray ionization ion trap mass spectrometry (ESI/ITMS) of simple organophosphorus compounds [1] demonstrated that detailed structural information could be obtained by sequential fragmentation of the ions using collision induced dissociation (CID). Several novel fragmentations/rearrangements were observed and it was apparent that the full potential of this approach could not be exploited until a more detailed understanding of the ion fragmentations was obtained. Such an understanding will only result from a detailed study of a wide range of compounds. The present paper describes the investigation of two isomeric organophosphates of particular relevance to chemical warfare convention (CWC) considerations.     

Dianion metallation reactions of n,n-dimethylvanillylamine and n,n-dimethylisovanillylamine

The utility of dianion chemistry in the synthesis of polyfunctional aromatics is demonstrated by the direct lithiation of the vanillylamine 1 and by the metal-halogen exchange reaction of the bromo isovanillylamines 9 and 10.     

The generation and photochemistry of indenone o-oxide and fluorenone o-oxide in low temperature matrices

The photolysis of diazoindene and diazofluorene at 12K in N₂ matrices containing O₂ has been studied, using i.r. spectroscopy. The carbonyl oxides, indenone $\text{O}$-oxide and fluorenone $\text{O}$-oxide, were formed by the reaction of O₂ with the corresponding carbenes, and under appropriate conditions could be detected as very photolabile species. Photolysis of indenone $\text{O}$-oxide gave indenone and isocoumarin; similar photolysis of fluorenone $\text{O}$-oxide gave fluorenone and dibenzopyran-6-one.     

Targeted and modular architectural polymers employing bioorthogonal chemistry for quantitative therapeutic delivery

There remain several key challenges to existing therapeutic systems for cancer therapy, such as quantitatively determining the true, tissue-specific drug release profile in vivo, as well as reducing side-effects for an increased standard of care. Hence, it is crucial to engineer new materials that allow for a better understanding of the in vivo pharmacokinetic/pharmacodynamic behaviours of therapeutics. We have expanded on recent “click-to-release” bioorthogonal pro-drug activation of antibody-drug conjugates (ADCs) to develop a modular and controlled theranostic system for quantitatively assessing site-specific drug activation and deposition from a nanocarrier molecule, by employing defined chemistries. The exploitation of quantitative imaging using positron emission tomography (PET) together with pre-targeted bioorthogonal chemistries in our system provided an effective means to assess in real-time the exact amount of active drug administered at precise sites in the animal; our methodology introduces flexibility in both the targeting and therapeutic components that is specific to nanomedicines and offers unique advantages over other technologies. In this approach, the in vivo click reaction facilitates pro-drug activation as well as provides a quantitative means to investigate the dynamic behaviour of the therapeutic agent.

There remain several key challenges to existing therapeutic systems for cancer therapy, such as quantitatively determining the true, tissue-specific drug release profile in vivo, as well as reducing side-effects for an increased standard of care.     

The solvent extraction of metal complexes of pyridine-2-aldehyde-2'-pyridylhydrazone

The distribution behaviour of the complexes formed between the terdentate ligand, pyridine-2-aldehyde-2'-pyridylhydrazone, and Zn(II), Cd(II), Fe(II), Cu(II), Ni(II), Mn(II) and Pd(II) has been studied between aqueous buffer and chloroform. Results are interpreted in terms of the complexes in the aqueous solution and the loss of a proton from each coordinated ligand to form an uncharged, extractable species. The suitability of PAPHY as a spectrophotometric reagent used in conjunction with a solvent extraction procedure is discussed.