A Theoretical investigation of a potential high energy density compound 3,6,7,8-tetranitro-3,6,7,8-tetraaza-tricyclo[3.1.1.1(2,4)]octane

The B3LYP/6-31G (d) density functional theory (DFT) method was used to study molecular geometry, electronic structure, infrared spectrum (IR) and thermodynamic properties. Heat of formation (HOF) and calculated density were estimated to evaluate detonation properties using Kamlet-Jacobs equations. Thermal stability of 3,6,7,8-tetranitro-3,6,7,8-tetraaza-tricyclo [3.1.1.1(2,4)]octane (TTTO) was investigated by calculating bond dissociation energy (BDE) at the unrestricted B3LYP/6-31G(d) level. Results showed the N-NO2 bond is a trigger bond during the thermolysis initiation process. The crystal structure obtained by molecular mechanics (MM) methods belongs to P2(1)/C space group, with cell parameters a = 8.239 Å, b = 8.079 Å, c = 16.860 Å, Z = 4 and r = 1.922 g cm-3. Both detonation velocity of 9.79 km s-1 and detonation pressure of 44.22 GPa performed similarly to CL-20. According to the quantitative standards of energetics and stability, TTTO essentially satisfies this requirement as a high energy density compound (HEDC).

Biheterocyclic ligands: synthesis, characterization and coordinating properties of bis(4-amino-5-mercapto-1,2,4-triazol-3-yl) alkanes with transition metal ions and their thermokinetic and biological studies

The Co(II), Ni(II) and Cu(II) metal ions complexes of Bis(4-amino-5-mercapto-1,2,4-triazol-3-yl) alkanes (BATs) have been prepared and characterized by elemental analysis, conductivity measurements infrared, magnetic susceptibility, the electronic spectral data and thermal studies. Based on spectral and magnetic results, the ligands are tetradentate coordinating through the N and S-atoms of BATs; six-coordinated octahedral or distorted octahedral and some times four-coordinated square planar were proposed for these complexes. Activation energies computed for the thermal decomposition steps were compared. The ligands and their metal complexes were tested in vitro for their biological effects. Their activities against two gram-positive, two gram-negative bacteria and two fungal species were found to vary from moderate to very strong.

1.° Ordinis Cisterciensis origo, statuta, usus et officia ecclesiastica. — 2.° Ivonis, Carnotensis, epistolae. — 3.° Ejusdem sermones. — 4.° Lucii, Papae, et aliorum rescripta pro monasterio Lirensi. — 5.° Vetus librorum ejusdem monasterii catalogus. — 6.° Liber censuum et ecclesiarum ad idem monasterium pertinentium

Puteanus

1.° Martyrologium Usuardi. — 2.° Regula S. Benedicti. — 3.° Lectiones evangeliorum per anni circulum. — 4.° Necrologium Prioratus S. Roberti Conillonis, sive Cornillonis, prope Gratianopolim. — 5.° Liber prosarum S. Mariae Virginis.

Colbertinus

1.° Passio sancti Sixti et sociorum. — 2.° Passio sancti Laurentii. — 3.° Passio sancti Hippolyti. — 4.° Passio sanctorum Abdon et Sennes. — 5.° Passio sancti Symphoriani. — 6.° Passio sanctorum Timothei et Apollinaris. — 7.° Passio sanctae Susannae, Virginis. — 8.° Passio sancti Antonini. — 9.° Vita sancti Barsanorii, Abbatis. — 10.° Vita sancti Nicolai, Myrensis Episcopi. — 11.° Narratio de ejusdem translatione : authore Joanne, Archidiacono Barrensi. — 12.° Vita sancti Leonardi. — 13.° Vita sancti Odonis, Abbatis : authore Joanne, Monacho. — 14.° Vita beati Majoli : authore Odilone, Presbytero. — 15.° Vita beati Odilonis, Abbatis : authore Petro Damiano. — 16.° Vita sancti Tetbaldi, Confessoris. — 17.° Vita Euphimiani, servi Dei. — 18.° Passio S. Eustachii et uxoris ejus. — 19.° Vita sancti Romani, Rothomagensis Archiepiscopi. — 20.° Bedae, Presbyteri, tractatus in Proverbia Salomonis : initium tantùm superest.

Bigotianus

1.° Vita et gesta sancti Pardulfi, Confessoris. — 2.° Passio sancti Barnabae. — 3.° Canticum canticorum. — 4.° Proverbia Salomonis. — 5.° Ecclesiastes. — 6.° Anonymi commentarius in Canticum canticorum ; incipit : Vox Ecclesiae. — 7.° Liber Sapientiae. — 8.° Ecclesiasticus. — 9.° Vita sancti Martialis, Apostoli. — Initio voluminis folia quaedam reperias è quibus constat veteri Ecclesiae consuetudine plures Sacerdotes administrando Extremaeunctionis sacramento olim interfuisse, et suam singulos orationem et benedictionem pronunciasse. — Hujusce codicis pars decimo, pars decimo tertio saeculo videtur exarata.

Sancti Martialis Lemovicensis

1.° Galeni tractatus de qualitate herbarum et aromatum. — 2.° Epistola de phlebotomia. — 3.° Hippocratis epistola de eodem argumento. — 4.° Apollinis epistola de eodem argumento. — 5.° Vindiciani epistola de quatuor humoribus. — 6.° Anonymi medicinalis sententia de temporibus phlebotomiae. — 7.° Hippocratis epistola supposititia ad Antiochum, Regem. — 8.° Anonymi receptae variae. — 9.° Galeni de ephemeris febribus libri tres priores et initium quarti.

Philiberti de la Mare

1.° Apuleii, Madaurensis, Platonici Philosophi, liber de Deo Socratis. — 2.° Hermetis Trisinegisti Asclepius. — 3.° Apuleii liber de dogmate Platonis. — 4.° Ejusdem liber de philosophia. — 5.° Ejusdem liber de mundo.

Memmianus, antea coenobii Sancti Victoris Parisiensis

1.° Aurelii Clementis Prudentii carmina : passim inter lineas glossae et ad marginem scholia. — 2.° Servii, Grammatici, centimetrum. — 3.° Versiculi de decem plagis Aegypti et de septem diebus primordii mundi. — 4.° Aenigmata nonnulla. — 5.° Epitaphium Adalberonis, Metensis Episcopi. — 6.° Anonymi versus ad Ratramnum, Magistrum.

Colbertinus

Effects of sample solvent composition and injection volume on chromatographic peak profiles of methyl w- benzimidazolecarbamate and 3-butyl1-2,4-dioxo[1,2-a]-s- triazinobenzimidazole in RP-HPLC

The effects of sample solvent composition and the injection volume, on the chromatographic peak profiles of two carbamate derivatives, methyl 2-benzimidazolecarbamate (MBC) and 3-butyl-2,4-dioxo[1,2-a]-s-triazinobenzimidazole (STB), were studied using reverse phase high performance liquid chromatograph. The study examined the effects of acetonitrile percentage in the sample solvent from 5 to 50%, effects of methanol percentage from 5 to 50%, effects of pH increase from 4.42 to 9.10, and effect of increasing buffer concentration from ° to 0.12M. The effects were studied at constant and increasing injection mass and at four injection volumes of 10, 50, 100 and 200 uL. The study demonstrated that the amount and the type of the organic solvents, the pH, and the buffer strength of the sample solution can have a pronounced effect on the peak heights, peak widths, and retention times of compounds analysed. MBC, which is capable of intramolecular hydrogen bonding and has no tendency to ionize, showed a predictable increase .in band broadening and a decrease in retention times at higher eluting strengths of the sample solvent. STB, which has a tendency to ionize or to strongly interact with the sample solvent, was influenced in various ways by the changes in ths sample solvent composition. The sample solvent effects became more pronounced as the injection volume increased and as the percentage of organic solvent in the sample solution became greater. The peak height increases for STB at increasing buffer concentrations became much more pronounced at higher analyte concentrations. It was shown that the widely accepted procedure of dissolving samples in the mobile phase does not yield the most efficient chromatograms. For that reason samples should be dissolved in the solutions with higher aqueous content than that of the mobile phase whenever possible. The results strongly recommend that all the samples and standards, regardless whether the standards are external or internal, be analysed at a constant sample composition and a constant injection volume.

Enhanced Templating in the Crystallisation of Poly(E-caprolactone) Using 1,3:2,4-di(4-Chlorobenzylidene) Sorbitol

We show that small quantities of 1,3:2,4-di(4-chlorobenzylidene) sorbitol dispersed in poly(epsilon-caprolactone) provide a very effective self-assembling nanoscale framework which, with a flow field, yields extremely high levels of polymer crystal orientation. During modest shear flow of the polymer melt, the additive forms highly extended nano-particles which adopt a preferred alignment with respect to the flow field. On cooling, polymer crystallisation is directed by these particles. This chloro substituted dibenzylidene sorbitol is considerably more effective at directing the crystal growth of poly(epsilon-caprolactone) than the unsubstituted compound.

Ultrafast excited state dynamics controlling photochemical isomerization of N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium coordinated to a {Re-1(CO)(3)(2,2 '-bipyridine)} chromophore

Two Multifunctional photoactive complexes [Re(Cl)(CO)(3)-(MeDpe(+))(2)](2+) and [Re(MeDpe(+))(CO)(3)(bpy)](2+) (MeDpe(+) = N-methyl-4-[trans-2-(4-pyridyl)ethenyl]pyridinium, bpy = 2,2'-bipyridine) were synthesized. characterized. and their redox and photonic properties were investigated by cyclic voltammetry: ultraviolet-visible-infrared (UV/Vis/IR) spectroelectrochemistry, stationary UV/Vis and resonance Raman spectroscopy; photolysis; picosecond time-resolved absorption spectroscopy in the visible and infrared regions: and time-resolved resonance Raman spectroscopy. The first reduction step of either complex Occurs at about -1.1 V versus Fc/Fc(+) and is localized at MeDpe(+). Reduction alone does not induce a trans -> cis isomerization of MeDpe(+). [Re(Cl)(CO)(3)(MeDPe(+))(2)](2+) is photostable, while [Re(MeDpe(+))(CO)(3)(bpy)](2+) and free MeDpe(+) isomerize under near-UV irradiation. The lowest excited state of [Re(Cl)(CO)(3)(MeDPe(+))(2)](2+) has been identified as the Re(Cl)(CO)(3) -> MeDpe(+) (MLCT)-M-3 (MLCT = metal-to-ligand charge transfer), decaying directly to the ground state with lifetimes of approximate to 42 (73%) and approximate to 430ps (27%). Optical excitation of [Re(MeDpe(+))(CO)(3)(bpy)](2+) leads to population of Re(CO)(3) -> MeDpe(+) and Re(CO)(3) -> bpy (MLCT)-M-3 states, from which a MeDpe(+) localized intraligand 3 pi pi* excited state ((IL)-I-3) is populated with lifetimes of approximate to 0.6 and approximate to 10 ps, respectively. The 3IL state undergoes a approximate to 21 ps internal rotation, which eventually produces the cis isomer on a much longer timescale. The different excited-state behavior of the two complexes and the absence of thermodynamically favorable interligand electron transfer in excited [Re(MeDpe(+))(CO)(3)(bpy)](2+) reflect the fine energetic balance between excited states of different orbital origin, which can be tuned by subtle Structural variations. The complex [Re(MeDpe+)(CO)(3)(bpy)](2+) emerges as a prototypical, multifunctional species with complementary redox and photonic behavior.

Synthesis, structure, and redox states of homoleptic d-block metal complexes with bis-1,2,4-triazin-3-yl-pyridine and 1,2,4-triazin-3-yl-bipyridine extractants

it has been established that triazinyl bipyridines (hemi-BTPs) and bis-triazinyl pyridines (BTPs), ligands which are currently being investigated as possible ligands for the separation of actinides from lanthanides in nuclear waste, are able to form homoleptic complexes with first row transition metals such as cobalt(IT), copper(II), iron(II), manganese(II), nickel(II) and zinc(II). The metal complexes exhibit six-co-ordinate octahedral structures and redox states largely analogous to those of the related terpyridine complexes. The reactivity of the different redox states of cobalt bis-hemi-BTP complex in aqueous environments has been studied with two-phase electrochemistry by immobilisation of the essentially water-insoluble metal complexes on graphite electrodes and the immersion of this modified electrode in an aqueous electrolyte. It was found that redox potentials for the metal-centred reactions were pH-independent whereas the potentials for the ligand-centred reactions were strongly pH-dependent. The reductive degradation of these complexes has been investigated by computational methods. Solvent extraction experiments have been carried out for a range of metals and these show that cobalt(II) and nickel(II) as well as palladium(II), cadmium(II) and lead(II) were all extracted with the ligands 1e and 2c with higher distribution ratios that was observed for americium(III) under the same conditions. The implications of this result for the use of these ligands to separate actinides from nuclear waste are discussed. (c) 2005 Elsevier Ltd. All rights reserved.