Separation of Monovinyl and Divinyl Protochlorophyllides Using C30 Reverse Phase High Performance Liquid Chromatography Column: Analytical and Preparative Applications

A new, high performance liquid chromatography method has been developed for the separation of monovinyl- and divinyl-protochlorophyllides, using commercially available, C₃₀ reverse phase column and isocratic elution. This method can be used both for analytical applications and preparative scale purification of monovinyl- and divinyl-protochlorophyllides using the same column where submilimolar concentrations of the crude protochlorophyllide extract can be separated in one run. The purity of the obtained protochlorophyllides was demonstrated by spectroscopic methods, as well by the formation of aggregates in toluene.     

Gas-phase derivatization of [C3H5]+ ions using tandem mass spectrometry methods A13C labelling study

The study of specifically ¹³C-labelled precursors sheds further light on the gas-phase chemistry of allyl and 2-propenyl cations. It is demonstrated that both species are formed from allyl and 2-propenyl bromide upon 70 eV electron impact ionization without skeletal reorganization. Gas-phase derivatization of the [C₃ H₅]⁺ ions with benzene facilitates, as suggested and observed earlier, the distinction of the two isomers using collision-induced dissociation of the Wheland complexes (or isomers thereof). The ¹³C labelling data clearly demonstrate that 64% of allyl cations survive the derivatization while 36% isomerize to 2-phenylpropyl cations; the latter are also formed via the reaction of 2-propenyl cation with benzene, protonation of α-methylstyrene and water loss from protonated 2-phenyl-2-propanol, respectively. Unimolecular loss of C₂H₄ from protonated allylbenzene proceeds via two competing reaction channels: one involves heterolysis of 1-phenylpropyl cations (～30%); the major pathway (～70%), however, involves decomposition via propylene benzenium ions.     

Aerobic oxidation of methyl p-tolyl sulfide catalyzed by a remarkably labile heteroscorpionate RuII-aqua complex,fac-[RuII(H2O)(dpp)(tppm)]2+

fac-[RuII(Cl)(dpp)(L3)]+ (L3 = tris(pyrid-2-yl)methoxymethane (tpmm) = [1A]+ and tris(pyrid-2-yl)pentoxymethane (tppm) = [1B]+ and dpp = di(pyrazol-1-yl)propane) rapidly undergo ligand substitution with water to form fac-[RuII(H2O)(dpp)(L3)]2+ (L3 = tpmm = [2A]2+ and tppm = [2B]2+). In the structure of [2A]2+, the distorted octahedral arrangement of ligands around Ru is evident by a long Ru(1)-O(40) of 2.172(3) A and a large angle O(40)-Ru(1)-N(51) of 96.95(14) degrees . The remarkably short distance between O(40) of H2O and H(45a) of dpp confirms the heteroscorpionate ligand effect of dpp on H2O. [2B]2+ aerobically catalyzes methyl p-tolyl sulfide to methyl p-tolyl sulfoxide in 1,2-dichlorobenzene at 25.0 +/- 0.1 degrees C under 11.4 psi of O2. Experimental facts in support of this aerobic sulfide oxidation are the absence of H2O2 and the oxidative reactivity of the putative Ru(IV)-oxo intermediate toward methyl p-tolyl sulfide, 2-propanol, and allyl alcohol. This study provides the first documented example of aerobic-sulfide oxidation catalyzed by the remarkably labile heteroscorpionate Ru(II)-aqua complex without the formation of a highly reactive peroxide as an intermediate.     

EFFICACY OF PHOTODYNAMIC THERAPY ON ORIGINAL AND RECURRENT RAT MAMMARY TUMORS

Abstract— Photodynamic therapy has demonstrated efficacy toward primary, metastatic and recurrent human tumors. Here, we investigated the ability of photodynamic therapy, using Photofrin, to inhibit growth of R3230AC mammary adenocarcinomas when tumors were treated as original implants and again as lesions recurring at the initial treatment site. The results demonstrate that both initial implants and lesions recurring after the first photodynamic treatment respond similarly to the same photodynamic therapy protocol, with mean tumor volume doubling times of ˜ 11 days in both cases. Cells cultured from original tumor implants or tumors that recurred after photodynamic treatment accumulate equivalent amounts of [¹⁴C]polyhematoporphyrin. Single cell suspensions prepared from either original or recurrent tumors from animals administered 5 mg/kg Photofrin and exposed to light in vitro displayed comparable phototoxicity. Additionally, examination of tumors by light microscopy revealed no morphological differences between the original tumor implants and the recurrent lesions. Taken together, these data indicate that lesions which recurred at the site of the initial photodynamic treatment were not resistant to a second identical course of photodynamic therapy.     

Fluorescence lifetimes and spectral properties of protochlorophyllide in organic solvents in relation to the respective parameters in vivo

In this work, absorption and fluorescence spectra of protochlorophyllide (Pchlide), as well as its fluorescence lifetime, were investigated in organic solvents having different physical properties. The obtained Pchlide spectral features are discussed in relation to the parameters describing solvent properties (refractive index and dielectric constant) and taking into account the specific solvent-Pchlide interaction. The correlation of Pchlide Qy and Soret absorption bands with solvent polarizability function ((n2 - 1)/(n2 + 2)) has been found; however, the dispersion of the observed points was rather high. A small Stokes shift of a magnitude between 50 and 300 cm(-1) was found, which indicates low sensitivity of Pchlide to nonspecific solvation. The fluorescence decay of Pchlide was single exponential in all the investigated solvents, with the lifetime value ranging from 5.2 ns for dioxane to 3.5 ns for methanol. Dependence of the obtained fluorescence lifetimes on the solvent orientation polarizability, a parameter being the function of both refractive index and dielectric constant, was discussed. In water-methanol mixtures, a further decrease of the fluorescence lifetime was observed, giving values of 2.9 ns for 25% methanol. Double-exponential decay of Pchlide fluorescence was found for Pchlide in a solution of 15% methanol with the lifetimes of 4.5 +/- 0.5 ns and 1.2 +/- 0.3 ns and in pure water with the lifetimes of 2.5 +/- 0.5 ns and 0.4 +/- 0.1 ns. The obtained results are discussed in relation to spectroscopic properties of Pchlide in vivo.     

The remarkable reactivity of high oxidation state ruthenium and osmium polypyridyl complexes

There is a remarkable redox chemistry of higher oxidation state M(IV)-M(VI) polypyridyl complexes of Ru and Os. They are accessible by proton loss and formation of oxo or nitrido ligands, examples being cis-[RuIV(bpy)2(py)(O)]2+ (RuIV=O2+, bpy=2,2'-bipyridine, and py=pyridine) and trans-[OsVI(tpy)(Cl)2(N)]+ (tpy=2,2':6',2' '-terpyridine). Metal-oxo or metal-nitrido multiple bonding stabilizes the higher oxidation states and greatly influences reactivity. O-atom transfer, hydride transfer, epoxidation, C-H insertion, and proton-coupled electron-transfer mechanisms have been identified in the oxidation of organics by RuIV=O2+. The Ru-O multiple bond inhibits electron transfer and promotes complex mechanisms. Both O atoms can be used for O-atom transfer by trans-[RuVI(tpy)(O)2(S)]2+ (S=CH3CN or H2O). Four-electron, four-proton oxidation of cis,cis-[(bpy)2(H2O)RuIII-O-RuIII(H2O)(bpy)2]4+ occurs to give cis,cis-[(bpy)2(O)RuV-O-RuV(O)(bpy)2]4+ which rapidly evolves O2. Oxidation of NH3 in trans-[OsII(tpy)(Cl)2(NH3)] gives trans-[OsVI(tpy)(Cl)2(N)]+ through a series of one-electron intermediates. It and related nitrido complexes undergo formal N- transfer analogous to O-atom transfer by RuIV=O2+. With secondary amines, the products are the hydrazido complexes, cis- and trans-[OsV(L3)(Cl)2(NNR2)]+ (L3=tpy or tpm and NR2-=morpholide, piperidide, or diethylamide). Reactions with aryl thiols and secondary phosphines give the analogous adducts cis- and trans-[OsIV(tpy)(Cl)2(NS(H)(C6H4Me))]+ and fac-[OsIV(Tp)(Cl)2(NP(H)(Et2))]. In dry CH3CN, all have an extensive multiple oxidation state chemistry based on couples from Os(VI/V) to Os(III/II). In acidic solution, the OsIV adducts are protonated, e.g., trans-[OsIV(tpy)(Cl)2(N(H)N(CH2)4O)]+, and undergo proton-coupled electron transfer to quinone to give OsV, e.g., trans-[OsV(tpy)(Cl)2(NN(CH2)4O)]+ and hydroquinone. These reactions occur with giant H/D kinetic isotope effects of up to 421 based on O-H, N-H, S-H, or P-H bonds. Reaction with azide ion has provided the first example of the terminal N4(2-) ligand in mer-[OsIV(bpy)(Cl)3(NalphaNbetaNgammaNdelta)]-. With CN-, the adduct mer-[OsIV(bpy)(Cl)3(NCN)]- has an extensive, reversible redox chemistry and undergoes NCN(2-) transfer to PPh3 and olefins. Coordination to Os also promotes ligand-based reactivity. The sulfoximido complex trans-[OsIV(tpy)(Cl)2(NS(O)-p-C6H4Me)] undergoes loss of O2 with added acid and O-atom transfer to trans-stilbene and PPh3. There is a reversible two-electron/two-proton, ligand-based acetonitrilo/imino couple in cis-[OsIV(tpy)(NCCH3)(Cl)(p-NSC6H4Me)]+. It undergoes reversible reactions with aldehydes and ketones to give the corresponding alcohols.     

Iminic N-bound iminophosphorano versus nitrilic n-bound iminophosphorano Os(IV) complexes: a new double derivatization of the nitrido ligand

The reactions between trans-[Os(IV)(tpy)(Cl)(2)(NCN)] (1) and PPh(3) and between trans-[Os(IV)(tpy)(Cl)(2)(NPPh(3))](+) (2) and CN(-) provide new examples of double derivatization of the nitrido ligand in an Os(VI)-nitrido complex (Os(VI)N). The nitrilic N-bound product from the first reaction, trans-[Os(II)(tpy)(Cl)(2)(NCNPPh(3))] (3), is the coordination isomer of the first iminic N-bound product from the second reaction, trans-[Os(II)(tpy)(Cl)(2)(N(CN)(PPh(3)))] (4). In CH(3)CN at 45 degrees C, 4 undergoes isomerrization to 3 followed by solvolysis and release of (N-cyano)iminophosphorane, NCNPPh(3). These reactions demonstrate new double derivatization reactions of the nitrido ligand in Os(VI)N with its implied synthetic utility.     

Reactions in aminosilane-epoxy prepolymer systems. II. Reactions of alkoxysilane groups with or without the presence of water

The hydrolysis and reactions of alkoxy silane groups have been studied on a model compound (TA) prepared from 2 mol of phenyl glycidyl ether and 1 mol of aminopropyl triethoxy silane. At low (40°C) and high (140°C) temperatures, the monomer conversion and the evolution of the molecular mass are followed by size exclusion chromatography (SEC). During the same reaction time, the evolution of the functional groups, hydroxyl CH? OH, ethoxy ? O? C₂H₅, and siloxane Si? O? Si, is observed by FTIR spectroscopy. Without the presence of water, reactions between hydroxyl and ethoxy silane lead to gelation at the end of the reaction. A by-product, probably a cyclic tetramer is also formed. After the hydrolysis, the reaction of the model compound is quite different. The product of reaction is always soluble, even after a treatment at high temperatures, and the evolution of the molecular mass versus the reaction time seems to correspond to the condensation giving a dead cyclic tetramer. From this study it is evident that the curing cycle has a great influence on the properties of the interface of a composite based on a epoxy matrix.     

Control synthesis of isocyanate and alkoxy-silane terminated macromers

The kinetics of the reactions in bulk of 4,4′-dicyclohexyl methane diisocyanate (H₁₂ MDI) and 5-isocyanato-1,3,3-trimethylcyclohexylmethyl isocyanate or isophorone diisocyanate (IPDI) with benzylic alcohol (BZA) and α-hydroxy-ω-methyl ether-terminated polyethylene oxide PEO (M?_w = 350) were studied by size exclusion chromatography (SEC) and ¹³C nuclear magnetic resonance (¹³C-NMR). The substitution effect is exhibited in the case of H₁₂ MDI reactivity. The kinetic constants were calculated by a numerical method. The second-order kinetic mechanism was shown to be valid. In the IPDI case, the cycloaliphatic isocyanate group is shown to be more reactive than the aliphatic group in our conditions, without catalysis, in agreement with previous results from the literature, in our obtained by ¹H-and ¹³C-NMR without any catalyst. The reactivity ratio is found to be on the order of 3. This difference in reactivity of the two isocyanate groups is used for the control synthesis of isocyanate and alkoxy-silane-terminated macromers.     

Os(II)-nitrosyl and Os(II)-dinitrogen complexes from reactions between Os(VI)-nitrido and hydroxylamines and methoxylamines

Reactions between the Os(VI)-nitrido salts (e.g., trans-[Os(VI)(tpy)(Cl)(2)(N)]PF(6) (tpy = 2,2':6',2"-terpyridine), cis-[Os(VI)(tpy)(Cl)(2)(N)]PF(6), and fac-[Os(VI)(tpm)(Cl)(2)(N)]PF(6) (tpm = tris(pyrazol-1-yl)methane)) and the hydroxylamines (e.g., H(2)NOH and MeHNOH) and the methoxylamines (e.g., H(2)NOMe and MeHNOMe) in dry MeOH at room temperature give three different types of products. They are Os(II)-dinitrogen (e.g., trans-, cis-, or fac-[Os(II)-N(2)]), Os(II)-nitrosyl [Os(II)-NO](+) (e.g., trans- or cis-[Os(II)-NO](+)), Os(IV)-hydroxyhydrazido (e.g., cis-[Os(IV)-N(H)N(Me)(OH)](+)), and Os(IV)-methoxyhydrazido (e.g., trans-/cis-[Os(IV)-N(H)N(H)(OMe)](+), and trans-/cis-[Os(IV)-N(H)N(Me)(OMe)](+)) adducts. The products depend in a subtle way on the electron content of the starting nitrido complexes, the nature of the hydroxylamines, the nature of the methoxylamines, and the reaction conditions. Their appearance can be rationalized by invoking the formation of a series of related Os(IV) adducts which are stable or decompose to give the final products by two different pathways. The first involves internal 2-electron transfer and extrusion of H(2)O, MeOH, or MeOMe to give [Os(II)-N(2)]. The second which gives [Os(II)-NO](+) appears to involve seven-coordinate Os(IV) intermediates based on the results of an (15)N-labeling study.