Facile one-pot preparation of thermally and photochemically convertible soluble precursors of copper phthalocyanine and naphthalocyanine

Soluble copper phthalocyanine (CuPc) and naphthalocyanine (CuNc) precursors which can be converted thermally and photochemically into insoluble CuPc and CuNc, respectively, have been synthesized by a one-step reaction using commercially available chemicals.     

Nano-SIMS analysis of Mg, Sr, Ba and U in natural calcium carbonate.

Concentrations of minor (Mg and Sr) and trace (Ba and U) elements in four natural calcium carbonate samples were first analyzed by inductively coupled plasma mass spectrometry (ICP-MS) after chemical dissolution and calibrated against a standard dolomite. Their homogeneities were checked by in situ laser ablation (LA) ICP-MS with 10-20 spots. The carbonate samples were measured by using a high lateral resolution secondary ion mass spectrometer (Nano-SIMS NS50). A approximately 4 nA O- primary beam was used to sputter a 5-6-microm diameter crater on the sample surface, and secondary positive ions were extracted for mass analysis using an accelerating voltage of 8 kV and a Mattauch-Herzog geometry. A multi-collector system was adjusted to detect 26Mg+, 43Ca+, 88Sr+, 138Ba+, 238U16O+ and 238U16O2+ ions at the same time. A resolving power of 2500-5000 at 10% peak height was attained by an entrance slit set at 40 microm, and each exit slit at 50 microm with adequate flat-topped peaks. The observed 26Mg/43Ca, 88Sr/43Ca, 138Ba/43Ca and 238U16O2/43Ca ratios agreed well with those measured by LA-ICP-MS. Foraminifera shells were analyzed at 5-6 microm scale by Nano-SIMS. There was a large variation of the Mg/Ca ratios, up to +/- 38%, even in a single fragment of the shell, suggesting that although the ratios provide a useful paleoceanographic proxy at bulk scale, they may reflect a more complex pattern at < 10 microm scale.     

Voltammetric homogeneous binding assay of biotin without a separation step using iminobiotin labeled with an electroactive compound.

Avidin, which is one type of glycoprotein, has a strong affinity with biotin (Ka = 10(15) M(-1)). Iminobiotin also forms a complex with avidin (Ka = 10(8) M(-1) at pH 9.5). The avidin-iminobiotin complex changes to the avidin-biotin complex in the presence of biotin because of the difference of the binding constant to avidin. In this study, the interaction between avidin and iminobiotin labeled with an electroactive compound was investigated by voltammetry. After avidin and the labeled iminobiotin (LI) were incubated in 0.1 M phosphate buffer (pH 7.0), the peak currents of LI were measured in various concentrations of biotin. The peak currents increased with increasing the concentration of biotin. Thus, this observation indicates the formation of avidin-biotin complex. On the other hand, the formation of avidin-iminobiotin complex depended on the pH of the solution. LI combines with the avidin at pH 5.6-8.9 and dissociates at pH 4.6.     

Concentration dependence of electroosmosis and streaming potential across charged membranes

Electroosmosis and streaming potential measurements were carried out across charged membranes made of collodion and sulfonated polystyrene. Experiments were confined to the range where linear flux/force relationships hold. Saxén's relationship holds between electroosmosis and streaming potential; for porous charged membranes these exhibit an approximate inverse proportionality to ionic mobility at the limit of low electrolyte concentration. Both tend towards zero at the limit of high electrolyte concentration.     

Copper salt catalyzed addition of arylboronic acids to azodicarboxylates

The addition of arylboronic acids 1 to azodicarboxylates 2 in the presence of a catalytic amount of a copper salt under mild reaction conditions gives aryl-substituted hydrazines 3 in high yields. The reaction is tolerant of a wide variety of functional groups.     

Nuclear spin driven quantum tunneling of magnetization in a new lanthanide single-molecule magnet: bis(phthalocyaninato)holmium anion

The first measurements of magnetization hysteresis loops on a diluted single crystal of [(Pc)2Ho]-.TBA+ (Pc = phthalocyaninato, TBA = tetrabutylammonium) in the subkelvin temperature range are reported. Characteristic staircase-like structure was observed, indicating the occurrence of the quantum tunneling of magnetization (QTM), which is a characteristic feature of SMMs. The quantum process in the new lanthanide SMMs is due to resonant quantum tunneling between entangled states of the electronic and nuclear spin systems, which is an essentially different mechanism from those of the known transition-metal-cluster SMMs. Evidence of the two-body quantum process was also observed for the first time in lanthanide complex systems.     

Catalytic [4+1] cycloaddition of alpha,beta-unsaturated carbonyl compounds with isocyanides

The GaCl(3)-catalyzed [4+1] cycloaddition reactions of alpha,beta-unsaturated ketones with isocyanides leading to lactone derivatives are described. While some other Lewis acids also show catalytic activity, GaCl(3) was the most efficient catalyst. The reaction is significantly affected by the structure of both the isocyanides and the alpha,beta-unsaturated ketones. Aromatic isocyanides, especially sterically demanding ones and those bearing an electron-withdrawing group, can be used, but aliphatic isocyanides cannot. The bulkiness of substituents at the beta-position of acyclic alpha,beta-unsaturated ketones is an important factor for the reaction to proceed efficiently. Generally, the more the bulky substituent, the higher is the yield. The reaction of alpha,beta-unsaturated ketones bearing geminal substituents at the beta-position gave the corresponding products in high yields. In monosubstituted derivatives, the yields are relatively low. However, substrates having a bulky substituent, such as a tert-Bu group, at the beta-position give high yields. Bulkiness is also required in cyclic alpha,beta-unsaturated ketones, but the effect is small. In alkyl vinyl ketones, the reactivity decreased with the steric bulk of the alkyl group. In aryl vinyl ketones, the presence of an electron-donating group on the aromatic ring decreases the reactivity. The success of the catalysis can be attributed to the low affinity of GaCl(3) toward heteroatoms, compared with usual Lewis acids.     

Energy transfer in the doped poly(N-Vinylcabazole)films

The energy transfer process to guest molecule5 m poly(N-vinylcarbJZole) films WJS directly nir.isurcd In (lie film con- taining pciylencihc sandwich excimer site opcralcs as an cncrEy donor, while the evciple't si-itc composed ofthccaiba2olc- dirnettiyl IcrcphtliaJate pair is fornied by trapping tlie migrating monomer fluorescent state.