Alkyl chain length dependence of the self-organized structure of alkyl-substituted phthalocyanines

The alkyl chain length on alkyl-substituted phthalocyanines (C(n)OPc) dependence of their self-organized structures was examined in this study. STM results indicated that the symmetry of ordered structures decreased as the alkyl chain became longer, with the exception of C(6)OPc, which preferentially formed a quasi-3-fold symmetrical structure. This could be explained by the fact that the C(n)OPc molecules are most likely to form densely packed structures. With C(n)OPc, when n = 4 to 10, the self-organized structures were dependent on the competition between how densely the molecules were arranged and how loose the intermolecular interaction energy was, caused by the formation of the densely packed structure. However, with C(n)OPc, when n = 10-18, the molecules tended to form densely packed structures by reducing the symmetry, even though the C(n)OPc molecules were distorted. When C(12)OPc and cobalt phthalocyanine were coadsorbed, the mixed system exhibited a four-fold symmetrical structure, which is rarely observed in C(12)OPc.     

Structures of two haptotropic isomers generated by the sliding of 1,3,5-triene ligands on a Pd-Pd-Pd chain

Two haptotropic isomers of [Pd(3)(mu(3)-DMVC)(2)(CH(3)CN)(2)][BF(4)](2) (DMVC = 1,2-di-(E)-carbomethoxyvinylcyclopentene) were structurally determined by X-ray crystallographic analyses; a monoclinic crystal contained a symmetric sandwich complex (mu(3)-eta(2):eta(2):eta(2)-coordination of DMVC ligands) and a triclinic crystal contained an unsymmetric sandwich complex (mu(3)-eta(2):eta(3):eta(1)-coordination of DMVC ligands), where the latter are connected to each other by C-HO hydrogen bonds.     

Design of biomolecular interface for detecting carbohydrate and lectin weak interactions

A hybrid functional biomolecular interface designed at a molecular size level is very effective at capturing an analyte with high sensitivity even if the interaction is very weak, as when detecting proteins with carbohydrate. We designed and processed a protein (lectin) recognition molecular interface taking the following points into consideration: (1) the height (molecular length) difference between the capturing and spacer molecules; (2) the ratio of capturing molecules in the recognition interface. When the height difference between the maltoside part (Concanavalin A (Con A) recognition group) and the OH group terminated spacer molecules exceeded (>(CH(2))(6)), the association rate constant (k(a)) became larger (k(a)(1/Ms): ～2.6 times) and the dissociation constant (K(D)) became much smaller (K(D)(M): 1.0 × 10(-6): ～0.17 times) compared with the similar heights (lengths) of both molecular interfaces. With regard to maltoside density, a 100% maltoside monolayer was unsuitable for detecting Con A. We constructed a nanostructured recognition site with a maltoside part of 10%, which was the most suitable ratio for Con A detection. The binding interaction between Con A and the maltoside group was changed from monovalent binding to bivalent binding when the maltoside part was diluted in the recognition interface. From electrochemical measurements, even though there was a small amount of maltoside component on the suitable recognition monolayer, quality similar to that of 100% maltoside was observed.     

Interfacial behavior of tetrapyridylporphyrin monolayer arrays

The behavior of monolayer films of free base 5,10,15,20-tetrapyridylporphinato (TPyP) and 5,10,15,20-tetrapyridylporphinato zinc(II) (ZnTPyP) on pure water, 0.1 M CdCl2, and 0.1 M CuCl2 subphases was investigated by surface pressure-area isotherms, specular X-ray reflectometry, and polarized total reflection X-ray absorption spectroscopy (PTRXAS). Surface pressure-area isotherms showed significant differences in the area per molecule on pure water compared to that on salt subphases, with a marked increase in the area observed on the salt solutions. This behavior was noted for both forms of the porphyrin and both salts investigated. Modeling of specular X-ray reflectometry data indicated that thinner and more electron dense layers on salt subphases best fit the observed profiles. These data suggest that the porphyrin macrocycle is oriented parallel to the interface on salt subphases and takes on a tilted conformation on pure water. In the case of ZnTPyP, PTRXAS was used to determine the orientation of the porphyrin moiety relative to the surface and to probe the coordination of the central Zn ion. In agreement with the pressure-area isotherms and reflectometry, the PTRXAS data indicate a change in orientation on the salt subphases.     

Separation and determination of basic dyes formulated in hair care products by capillary electrophoresis

A capillary electrophoretic (CE) method for analyzing five basic dyes (Basic Red 76, Basic Brown 16, Basic Yellow 57, Basic Brown 17 and Basic Blue 99) sold under the trade name Arianor, which are commonly used in hair care products, has been established. A buffer of 100 mM acetic acid-ammonium acetate (50:50) containing 90% (v/v) methanol was employed in a fused-silica capillary of 40.0 cm x 50 microm I.D. with a bubble cell arrangement. Washing the capillary end immediately after injection was effective in preventing peak tailing of the basic dyes, which was due to their adsorption onto the outer wall of the capillary during the injection. Under these optimized conditions, acceptable results for reproducibility, limit of detection and quantitation, and linearity were obtained for the five authentic dyes tested. The recoveries of five authentic basic dyes spiked to three commercial hair care products also provided with acceptable results. This optimized CE method is useful for the analysis of mixed basic dyes in hair care products.     

Electrochemical performance of angstrom level flat sputtered carbon film consisting of sp2 and sp3 mixed bonds

We have developed ultra-flat carbon film electrodes with a wide potential window and a low capacitive current by the electron cyclotron resonance (ECR) sputtering method. The film consists of sp2 and sp3 bonds (sp3/sp2 ratio = 0.702) and is sufficiently conductive for electrochemical measurements without doping. The film has average roughness of 0.7 A, which is much flatter than that of nanocrystalline diamond film. The potential limit of ECR sputtered carbon (current limit < +/-500 muA/cm2) in the positive direction is 2.0 V vs Ag/AgCl, which is slightly lower than that of boron-doped diamond (2.1 V) and much wider than that of a glassy carbon (GC) electrode (1.7 V). In contrast, a much wider potential window can be obtained in the negative direction. The capacitive current is also much lower than that of a GC electrode due to the ultra-flat surface and the low number of oxygen-containing groups at the film surface. ECR sputtered carbon film can be used to measure each base of oligonucleotides by electrochemical oxidation without any pretreatment. The ultra-flat surface and low surface oxygen concentration suppress fouling with electroactive species, such as oligonucleotides, NADH, and bisphenol A.