Detection of nitro-explosive compounds using derivatization and tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence

This thesis describes a novel approach towards the trace level detection of nitramine explosives, by exploring various reduction strategies and utilising ruthenium chemiluminescence. Synthesis of novel chemiluminescence compounds has been achieved, as well as the development of a detection method for determining the shelf life of ammunition.

Electrochemistry of tris(2,2′-bipyridyl) cobalt(II) in ionic liquids and aprotic molecular solvents on glassy carbon and platinum electrodes

The tris(2,2′-bipyridyl) complexes of cobalt(II) and (III) ([Co(bpy)3]^2+/3+) produce a redox couple of great interest in thermoelectrochemical cells and dye sensitized solar cells including both types of devices based on ionic liquid electrolytes. We present a systematic study of the electrochemistry of [Co(bpy)3]²⁺ [NTf2]^-2 in two ionic liquids (ILs) based on the 1-ethyl-3-methylimidazolium (C2mim) cation and two ILs based on the 1-butyl-1-methylpyrrolidinium cation (C4mpyr), as well as three aprotic molecular solvents. Platinum (Pt) and glassy carbon (GC) working electrodes were compared. In all solvents better electrochemical responses were observed on GC, which yielded higher currents in the cyclic voltammograms and lower rate constants for the redox reaction. The [Co(bpy)3]^1+/2+ couple is also readily observed, but this redox reaction is chemically irreversible, possibly because the [Co(bpy)3]¹⁺ complex dissociates. However, the [Co(bpy)3]^1+/2+ reaction is chemically reversible in all of the solvents studied, except 3-methoxypropionitrile, if excess of 2,2′-bipyridyl is added to the solution.

Chemiluminescence detection of MDMA in street drug samples using tris (2,2'-bipyridine) ruthenium (III)

Tris(2,2'-bipyridine)ruthenium(II) chemiluminescence was investigated for the detection of 3,4-methylenedioxymethamphetamine (MDMA) and several related compounds in street drug samples. Optimization using flow injection analysis showed that the selectivity of the reagent can be targeted towards the detection of secondary amines by altering the pH of the reaction environment. The greater selectivity of this mode of detection, compared to UV-absorbance, reduces the probability of false positive results from interfering compounds. The detection limit for MDMA under these conditions was 0.48 μM. A HPLC method incorporating post-column tris(2,2'-bipyridine)ruthenium(II) chemiluminescence detection was applied to the determination of MDMA in five street drug samples. The results obtained were in good agreement with quantification performed using traditional UV-absorbance detection, which demonstrates the viability of this method for confirmatory analysis of drug samples. This is the first report of tris(2,2'-bipyridine)ruthenium(II) chemiluminescence for the detection of MDMA and related amphetamine derivatives.

Electrogenerated chemiluminescence of tris(2,2' bipyridine)ruthenium(ii) using common biological buffers as co-reactant, pH buffer and supporting electrolyte

A series of aliphatic tertiary amines (HEPES, POPSO, EPPS and BIS-TRIS) commonly used to buffer the pH in biological experiments, were examined as alternative, non-toxic co-reactants for the electrogenerated chemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium(ii) ([Ru(bpy)3](2+)). These were found to be very attractive as "multi-tasking" reagents, serving not only as co-reactants, but also fulfiling the roles of pH buffer and supporting electrolyte within an aqueous environment; thus significantly simplifying the overall ECL analysis. Sub-nanomolar detection limits were obtained for [Ru(bpy)3](2+) in the presence of BIS-TRIS, making this species an valuable option for co-reactant ECL-based bioanalytical applications.

Phase behavior of the orange essential oil/sodium bis(2-ethylhexyl)sulfosuccinate/water system

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Estudo da microestrutura e dinâmica molecular do Poly(3-(2\'-ethylhexyl)thiophene)(P3EHT) via ressonância magnética nuclear

O estudo da microestrutura e dinâmica molecular de polímeros conjugados é de grande importância para o entendimento das propriedades físicas desta classe de materiais. No presente trabalho utilizou-se técnicas de ressonância magnética nuclear em baixo e alto campo para elucidar os processos de dinâmica molecular e cristalização do polímero Poly(3-(2’-ethylhexyl)thiophene) - P3EHT. O P3EHT é um polímero modelo para tal estudo, pois apresenta temperatura de fusão bem inferior a sua temperatura de degradação. Esta característica permite acompanhar os processos de cristalização in situ utilizando RMN. Além disso, sua similaridade ao já popular P3HT o torna um importante candidato a camada ativa em dispositivos eletrônicos orgânicos. O completo assinalamento do espectro de 13C para o P3EHT foi realizado utilizando as técnicas de defasamento dipolar e HETCOR. Os processos de dinâmica molecular, por sua vez, foram sondados utilizando DIPSHIFT. Observou-se um gradiente de mobilidade na cadeia lateral do polímero. Além disso, os baixos valores de parametros de ordem obtidos em comparação a experimentos similares realizados no P3HT na literatura indicam um aparente aumento no volume livre entre cadeias consecutivas na fase cristalina. Isso indica que a presença do grupo etil adicional no P3EHT causa um completo rearranjo das moléculas e dificulta seu empacotamento. Constatou-se ainda pouca variação das curvas de DIPSHIFT para os carbonos da cadeia lateral como função do método de excitação utilizado, o que aponta para um polímero que apresenta cadeia lateral móvel mesmo em sua fase cristalina. Os dados de dinâmica molecular foram corroborados por medidas de T1, T1ρ e TCH. Utilizando filtros dipolares em baixo campo observou-se três temperaturas de transição para o P3EHT: 250 K, 325 K e 350 K. A cristalização desse material é um processo lento. Verificou-se que o mesmo pode se estender por até até 24h a temperatura ambiente. Mudanças no espectro de 13C utilizando CPMAS em alto campo indicam um ordenamento dos anéis tiofeno (empacotamento π – π) como o principal processo de cristalização para o P3EHT.

Status assessment of toxic chemicals : tris(2,3-dibromopropyl) phosphate /

Mode of access: Internet.

Toxicological profile for di(2-ethylhexyl)phthalate /

"Prepared by Syracuse Research Corporation under contract no. 205-1999-00024; prepared for U.S. Dept. of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry."

Special occupational hazard review : alternatives to DI-2-ethylhexyl phthalate ("DOP")in respirator quantitative fit testing.

Mode of access: Internet.

Near-infrared emission from novel tris(8-hydroxyquinolinate)lanthanide(III) complexes-functionalized mesoporous SBA-15

A novel mesoporous material covalently bonded with 8-hydroxyquinoline (HQ) was synthesized (designated as Q-SBA-15). The 5-formyl-8-hydroxyquinoline grafted to.(3-aminopropyl)triethoxysilane, that is, alkoxysilane modified 8-hydroxyquinoline (Q-Si), was used as one of the precursors for the preparation of the Q-SBA-15 material. On the basis of the other function of the Q-Si of coordinating to lanthanide (Ln) ions, for the first time, the LnQ(3) complexes (Ln = Er, Nd, Yb) have been covalently bonded to the SBA-15 materials.

[Ru(bpy)(3)](2+)-doped silica nanoparticles within layer-by-layer biomolecular coatings and their application as a biocompatible electrochemiluminescent tag material

[Ru(bpy)(3)](2+)-doped silica (RuSi) nanoparticles were synthesized by using a water/oil microemulsion method. Stable electrochemiluminescence (ECL) was obtained when the RuSi nanoparticles were immobilized on a glassy carbon electrode by using tripropylamine (TPA) as a coreactant. Furthermore, the ECL of the RuSi nanoparticles with layer-by-layer biomolecular coatings was investigated. Squential self-assembly of the polyelectrolytes and biomolecules on the RuSi nanoparticles gave nanocomposite suspensions, the ECL of which decreased on increasing the number of bilayers.

Bis(2,2 '-bipyridine)(5,6-epoxy-5,6-dihydro-[1,10] phenanthroline)ruthenium: Synthesis and electrochemical and electrochemiluminescence characterization

In this work, an electrochemiluminescence (ECL) reagent bis(2,2'-bipyridine)(5,6-epoxy-5,6-dihydro-[1,10]phenanthroline)ruthenium complex (Ru-1) was synthesized, and its electrochemical and ECL properties were characterized. The synthesis of Ru-1 was confirmed by IR spectra, element analysis, and H-1 NMR spectra. For further study, its UV-vis absorption and fluorescence emission spectra were investigated. Ru-1 also exhibited quasi-reversible Ru-II/Ru-III redox waves in acetonitrile solution. The aqueous ECL behaviors of Ru-1 were also studied in the absence and in the presence of tripropylamine.