Rationalisation of weak ferromagnetism in manganese(III) chains: the relation between structure and ordering phenomena

The synthesis, structure and magnetic properties of the one-dimensional chain compounds [Mn(cyclam)(SO4)]ClO4.H2O (1) and [Mn(cyclam)(HCOO)](CF3SO3)(ClO4) (2) are reported. Cyclam is the cyclic tetradentate ligand 1,4,7,11-tetraazacyclotetradecane. Both chain compounds exhibit antiferromagnetic interactions within the chains. A magnetic ordering phase transition at 5.5 K in (1) is investigated by magnetisation measurements along the three principal crystallographic axes of a single crystal and the results show unambiguously that the ferromagnetic ordering is only taking place along one crystallographic axis. The spin structure of the magnetic ordered phase and the magnitude of the ferromagnetic moment are correlated with the crystal structure and symmetry of the compound.     

Kinetics and mechanism of the phenolysis of asymmetric diaryl carbonates

The reactions 4-methylphenyl 4-nitrophenyl carbonate (MPNPC), 4-chlorophenyl 4-nitrophenyl carbonate (CIPNPC), 4-methylphenyl 2,4-dinitrophenyl carbonate (MPDNPC), and 4-chlorophenyl 2,4-dinitrophenyl carbonate (CIPDNPC) with a homogeneous series of phenoxide anions are subjected to a kinetic investigation in aqueous solution (25.0 degrees C, ionic strength 0.2 M (KCI)). Under an excess of phenoxide with respect to the substrate, all of these reactions obey pseudo-first-order kinetics and are first order in phenoxide. The Br?nsted-type plots for the nucleophilic rate constants (k(N)) are linear, with slopes beta = 0.48 (MPNPC), 0.67 (ClPNPC), 0.41 (MPDNPC), and 0.32 (ClPDNPC). The magnitude of these slopes and the absence of a curvature in the Br?nsted plot at pK(a) = 7.1 for the CIPNPC reactions are consistent with concerted mechanisms (one step). The carbonates MPDNPC and ClPDNPC are more reactive than MPNPC and CIPNPC, respectively, toward phenoxide nucleophiles. This can be explained by the presence of a second nitro group in the nucleofuge of the dinitro derivatives, which (i) leaves their carbonyl carbon more positively charged, making them better electrophiles, and (ii) makes 2,4-dinitrophenoxide a better leaving group than 4-nitrophenoxide. The 4-chloro derivatives are more reactive than the corresponding 4-methyl derivatives. This should be due to the greater electron withdrawal of 4-chloro than 4-methyl, which makes the former carbonyl more electrophilic. Comparison of the concerted phenolysis of MPNPC with the stepwise reactions of secondary alicyclic amines with the same substrate indicates that substitution of a secondary alicyclic amine group in a zwitterionic tetrahedral intermediate by a phenoxy group greatly destabilizes the intermediate. An equation is deduced for log k(N) in terms of the basicity of the nucleophile, the nonleaving moiety, and the leaving group. This equation shows that for these reactions, the sensitivity of log k(N) to the basicity of the nonleaving moiety (beta(nlg) = -0.27) is very similar to that of the nucleofuge (beta(lg) = -0.25).     

Effect of ion pairing on steady-state voltammetric limiting currents at microelectrodes Part I. Theoretical principles

Voltammetric studies in solutions of high resistivity are facilitated by the use of microelectrodes under steady-state conditions. Such solutions are encountered with solvents of low permittivity because of the very sparing solubility of electrolytes. Moreover, in such media the supporting electrolyte, as well as the electroactive ionic species, is usually extensively ion paired. Here we predict the limiting current that will flow in these circumstances, when a monovalent ion undergoes a one-electron transfer at a hemispherical microelectrode to form a neutral product. The ion pairing equilibria are assumed to be fast but all diffusion coefficients are treated as distinct. An analytical solution is elusive in the general case, but a simple numerical procedure allows the limiting current to be predicted for any combination of the system parameters. Several special cases are also discussed, some of which yield explicit formulae for the limiting current. In a companion paper, experimental data are compared with the theoretical predictions.     

In situ monitoring of metal nanoparticle self-assembly on protein-functionalized glass by broadband optical waveguide spectroscopy

Broadband, time-resolved optical waveguide (OWG) spectroscopy has been used for in situ, real-time investigation into the self-assembly of metal nanoparticle monolayers. The OWG spectroscopy makes it possible to use the transverse electric (TE) and transverse magnetic (TM) modes to measure surface plasmon absorption of immobilized metal nanoparticles in two directions, parallel and normal to the waveguide surface. Therefore, this technique can provide direction-dependent information on the metal nanoparticles at the interface. In this paper, a 50-microm-thick glass plate was used as a slab waveguide and the kinetics of Au nanoparticle adsorption on a hemoglobin-functionalized glass substrate was examined in the early stage of self-assembly. The findings show that with the TE mode the surface plasmon resonance (SPR) behavior for immobilized Au nanoparticles is different from that with the TM mode.     

Crystal,Molecular, and Electronic Structure of 1-Acetyl-indoline and Derivatives

The crystal and molecular structures of the following molecules have been determined: 1-acetyl-indoline, 1-acetyl-5-nitro-indoline, l-acetyl-5-nitro-7-bromo-indoline, 1-acetyl-5-bromo-7-nitroindoline, and l-acetyl-5-bromo-7-nitro-indol. Molecular orbital calculations are performed for these compounds and two related species.     

New butenolides in plantlets of Virola surinamensis (Myristicaceae)

A phytochemical investigation in plantlets of the Brazilian medicinal tree Virola surinamensis resulted in the isolation and structural determination of four new compounds: 3-hydroxy-4-methyl-2-(11'-piperonyl-n-undecyl)-butenolide; 3-hydroxy-4-methyl-2-(7'-piperonyl-n-heptyl)-butanolide; 9'-(3,4-methylenedioxy-phenyl)-nonanoic acid and 13'-(3,4-methylene-dioxyphenyl)-tridecanoic acid. Thirteen compounds previously isolated from seeds and adult plants were also reported.     

Exciton dissociation dynamics in model donor-acceptor polymer heterojunctions. I. Energetics and spectra

In this paper we consider the essential electronic excited states in parallel chains of semiconducting polymers that are currently being explored for photovoltaic and light-emitting diode applications. In particular, we focus upon various type II donor-acceptor heterojunctions and explore the relation between the exciton binding energy to the band offset in determining the device characteristic of a particular type II heterojunction material. As a general rule, when the exciton binding energy is greater than the band offset at the heterojunction, the exciton will remain the lowest-energy excited state and the junction will make an efficient light-emitting diode. On the other hand, if the offset is greater than the exciton binding energy, either the electron or hole can be transferred from one chain to the other. Here we use a two-band exciton to predict the vibronic absorption and emission spectra of model polymer heterojunctions. Our results underscore the role of vibrational relaxation and suggest that intersystem crossings may play some part in the formation of charge-transfer states following photoexcitation in certain cases.     

Surface modification of proteins by covalent binding of acrylic polymers

Surface modification of enzymes for a potential use in therapy was obtained with a new type of tailor-made copolymers ofNacryloylmorpholine andN-acryloxysuccinimide. The first monomer was designed to confer solubility on the polymer, whereas the second was used to give it reactivity toward protein amino groups. The reactivity of polymers of different composition towards amino acid derivatives and model proteins, such as catalase and ribonuclease-A, is described. Water soluble and catalytically active enzyme derivatives were obained using copolymers prepared with a mixture of N-acryloxysuccinimide andn-acryloylmorpholine in a 1:99 molar ratio. At increasing molar ratio (3:97, 10:90) extensive crosslinking between polymer and enzymes takes place, yielding insoluble adducts.     

Effect of Photosensitizer Delivery System and Irradiation Parameters on the Efficiency of Photodynamic Therapy of B16 Pigmented Melanoma in Mice

Abstract— Previous studies (Biolo et al., Photochem. Photobiol. 59, 362-365, 1994) showed that liposome-delivered Si(IV)-na-phthalocyanine (SiNc) photosensitizes B16 pigmented melanoma subcutaneously transplanted in C57 mice to the action of 776 nm light. However, the efficacy of the phototreatment was limited by a lack of selectivity of tumor targeting by SiNc as well as by incomplete necrosis of the neoplastic mass. The present investigations show that the use of a different delivery system (Cremophor emulsion vs liposomes of dipalmitoylphosphatidylcholine) causes no significant increase in the selectivity of tumor targeting for three injected doses of SiNc (0.5, 1, 2 mg/kg). However, upon 776 nm light irradiation (300 mW/cm²; 520 J/cm²), the delay in the rate of tumor growth was maximal (7-8 days) for the highest naphthalocyanine dose. On the other hand, a remarkable improvement in the tumor response was obtained by inducing an intratumoral temperature increase to 44°C immediately after PDT. The thermal effect appeared to be due to photoexcitation of melanin by 776 nm light (550 mW/cm²; 520 J/cm²) and subsequent partial conversion of absorbed energy into heat.     

Spectroscopic and electrochemical studies on (2-hydroxypicolinate)-bis(2,2′-bipyridine)ruthenium(II) and related complexes

Summary The synthesis, spectra and electrochemistry of [Ru(bipy)₂-(picOH)]⁺ and -picO-[Ru(bipy)₂]₂ ²⁺ (bipy = 2,2-bipyridine and picOH = 3-hydroxypicolinate ion) are described. The spectroscopic properties in the visible region are dominated by the intense Ru bipy chargetransfer transitions. In the binuclear complex, the two [Ru(bipy)₂L]²⁺ moieties are nonequivalent, exhibiting E _1/2 = 0.69 and 1.20 V versus s.h.e. The partially oxidized species exhibits a weak intervalence transfer band at 1085 nm, and is consistent with a Robin-Day class II mixed valence complex.