Role of the spacer in the singlet-singlet energy transfer mechanism (Förster vs Dexter) in cofacial bisporphyrins

The cofacial bisporphyrins H4DPS (DPS = 4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene), H4DPO (DPO = 4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzofuran), H4DPX (DPX = 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene), H4DPA (DPA = 1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]anthracene), and H4DPB (DPB = 1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene) have been monometalated by Zn(OAc)2.2H2O and by GaCl3 to explore the singlet-singlet energy transfer from the photoexcited metal porphyrin center to the linked free base porphyrin. The spectroscopic (UV-vis and fluorescence) and photophysical properties (fluorescence lifetimes, tauF, and quantum yields, phiF) have been investigated at 298 and 77 K in degassed 2-MeTHF for the donor-acceptor systems, (Zn)H2DPS, (Zn)H2DPO, (Zn)H2DPA, (Zn)H2DPX, and (Zn)H2DPB, as well as for the bis-zinc complexes, (Zn)2DPS, (Zn)2DPO, (Zn)2DPX, and (Zn)2DPB, respectively, and the monoporphyrin derivatives, H2P, (Zn)P, and (Ga-OMe)P (P2- = 5-phenyl-2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrin-dianion). The singlet-singlet energy transfer rate constants (KET) were obtained using KET = (1/tauF -1/tauFo), where tauFo is the fluorescence lifetime of the corresponding bis-zinc(II) systems (or (Zn)P and (Ga-OMe)P) where no energy transfer occurs. The tauF value for three bis-zinc(II) compounds varies from 1.69 to 2.01 ns and is 1.84 (at 298 K) and 3.20 ns (at 77 K) for (Ga-OMe)P. In the donor-acceptor bismacrocycles, depending on the spacer and the temperature, the fluorescence lifetimes decrease down to 50-240 ps. The KET values range from approximately 4 to approximately 21 (ns(-1)) and have been analyzed considering both the F?rster and the Dexter mechanisms. Using the C(meso)-C(meso) distance parameters in the calculations, the F?rster and Dexter mechanisms operate for DPS and DPO, and for DPA, DPX, and DPB spacer systems, respectively. The limit distance where one mechanism dominates over the other is estimated to be around 5-6 A.     

Total synthesis of amaryllidaceae alkaloid buflavine

A concise synthesis of the amaryllidaceae alkaloid buflavine (1) and its regioisomer (2) involving sequential Meyers' biaryl coupling, enecarbamate formation, and hydrogenation followed by ultimate intramolecular reductive amination is presented.     

The asymmetric syntheses of the C-1 sidechains of zaragozic acid A and zaragozic acid C

The asymmetric syntheses of the C-1 sidechains of zaragozic acid A and C are described. Aldol reaction defines the chirality at C-4′and C-5′in two independent routes. Multigram preparation as well as a route amenable to derivatization are highlights of these approaches.     

Electron impact induced fragmentation of β-allenic and γ-acetylenic alcohols

The main fragmentation pathway of ionized hydroxyallenes (1) consists of a methyl loss. Extensive deuterium-labelling experiments indicate that the terminal allenic carbon is implied in this fragmentation. Collisional activation spectra indicate a propenyl-acylium structure (a) for these [M – CH₃]⁺ ions which can originate from a 1,4-hydroxyl migration followed by hydrogen rearrangements. Isomeric hydroxyacetylenes (2) behave similarly, also giving rise, by methyl loss, to acylium ions a. It is proposed that 2^{+ ˙} is irreversibly isomerized into 1^{+ ˙} by a 1,3-hydrogen transfer ‘catalysed’ by the hydroxy group. The proposed internal proton-bound complex justifies also the easier loss of water from 2⁺˙. Ethyl loss is also a prominent fragmentation for the hydroxyallene and hydroxy-acetylene homologues.     

Crotomacrine, a new clerodane diterpene from the fruits of Croton macrostachyus

A new clerodane diterpene, crotomacrine 1, together with the known crotepoxide were isolated from the fruits of Croton macrostachyus. Their structures were elucidated on the basis of spectral evidence.     

Properties of block and graft copolymers of polybutadiene with small complexed poly(4-vinylpyridine) segments

Various diblocks, triblocks and a graft copolymer of butadiene with 4-vinylpyridine short blocks have been prepared. They were complexed with ZnCl₂ to give ionomer-like materials. For all copolymers, the T_g of the elastomeric block (?84°C to ?91°C) was unchanged by complexation. For all diblocks and triblocks with short blocks (DP _n ～ 3) the storage modulus was only slightly increased by comparison with uncomplexed materials. For the graft copolymer even with short blocks the material is less sensitive to temperature after complexation. For triblocks, when the DP _n of the vinylpyridine blocks was high enough (15 units), complexes were associated in multiplets of large size and the elastomeric properties were retained up to 200°C.     

Novel heteroleptic cis-(C--N)2Pd(II) chelates for the preparation of enantiopure planar chiral cyclopalladated 2-[tricarbonyl(eta6-phenyl)chromium]pyridine

In the presence of large amounts of [Me4N]Cl, the reaction of ortho-chloromercurated 2-[(eta6-phenyl)tricarbonylchromium]pyridine with mu-chloro cyclopalladated aromatic compounds yields a series of new heteroleptic heterodinuclear cis-(C--N)2Pd(II) complexes, which are valuable precursors of planar chiral cyclopalladated (eta6-arene)Cr(CO)3 complexes.     

Polyelectrolyte multilayers and degradable polymer layers as multicompartment films

Polyelectrolyte multilayers are now a well established concept with numerous potential applications in particular as biomaterial coatings. To timely control the biological activity of cells in contact with a substrate, multicompartment films made of different polyelectrolyte multilayers deposited sequentially on the solid substrate constitute a promising new approach. In a first paper (Langmuir 2004, 20, 7298) we showed that such multicompartment films can be designed by alternating exponentially growing polyelectrolyte multilayers acting as reservoirs and linearly growing ones acting as barriers. In the present study, we first demonstrate however that these barriers composed of synthetic polyelectrolytes are not degraded despite the presence of phagocytic cells. We propose an alternative approach where exponentially growing poly(L-lysine)/hyaluronic acid (PLL/HA) multilayers, used as reservoirs, are alternated with biodegradable polymer layers consisting in poly(lactic-co-glycolic acid) (PLGA) and acting as barriers for PLL chains that diffuse within the PLL/HA reservoirs. We first show that these PLGA layers can be deposited alternatively with PLL/HA multilayers leading to polyelectrolyte multilayer/hydrolyzable polymeric layer films and acting as a reservoirs/barriers system. Bone marrow cells seeded on these films ending by a PLL/HA reservoir rapidly degrade it and internalize the PLL chains confined in this reservoir. Then the cells degraded locally the PLGA barrier and internalize the PLL localized in a lower (PLL/HA) compartment after 5 days of seeding. By changing the thickness of the PLGA layer, we hope to be able to tune the time delay of degradation. Such mixed architectures made of polyelectrolyte multilayers and hydrolyzable polymeric layers could act as coatings allowing us to induce a time scheduled cascade of biological activities. We are currently working on the use of comparable films with compartments filled by proteins or peptides and in which the degradation of the barriers results from a hydrolysis over tunable time scales.     

Triplet state properties of the benzo[α]pyrene-DNA complex as determined by optically detected zero-field magnetic resonance

The zero-field transitions in the photoexcited triplet state of benzo[α]pyrene bound to DNA have been observed by optical detection of magnetic resonance of 2 K. The transition frequencies individual spin sublevel intersystem crossing rates were measured by monitoring the microwave-induced intensity changes of the triplettriplet absorption at 465.8 nm. The triplet state zero-field splitting and dynamics for the benzo[α]pyrene DNA complex are compared with these properties measured for benzo(α)pyrene in other solvent systems.     

Komplexometrische Bestimmung von Metallkationenverunreinigungen in Reinchemikalien

Zusammenfassung Ein Verfahren zur quantitativen summarischen Bestimmung von Metallionenverunreinigungen in flüssigen Chemikalien (Reinheitsprüfung) durch komplexometrische Titration mit photometrischer Endpunktsanzeige wird beschrieben. Als Indikator dient Eriochromschwarz T; erfaßbar ist zirka 1 g in 20 ml. Durch einfaches Einengen des Ausgangsmaterials lassen sich noch Metallionengehalte von 0,01 ppm mit einer Genauigkeit von einigen Prozent bestimmen.

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Summary A procedure is described for the quantitative summary determination of metal ion impurities in liquid chemicals (purity tests) through complexo-metric titration with photometric endpoint indication. Eriochrome black T serves as indicator. Approximately 1 g can be detected in 20 ml. Metal ion contents as low as 0.01 ppm can still be determined with a precision of several per cent by simple concentration of the starting material.

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Résumé On décrit un procédé de dosage total quantitatif des impuretés à l'état d'ions métalliques dans les produits chimiques liquides (contrôle de la pureté) par titrage complexométrique avec détection du point équivalent par photométrie. On utilise le noir ériochrome T comme indicateur. La limite de dilution est d'environ 1 g/20 ml. On peut encore doser des teneurs en ions métalliques de 0,01 ppm avec une erreur de quelques pour cent simplement en diminuant la quantité initiale de substance.