Design and synthesis of labeling reagents (MS probes) for highly sensitive electrospray ionization mass spectrometry and their application to the detection of carbonyl, alcohol, carboxylic acid and primary amine samples.

Novel labeling reagents, called MS probes, which possess a positively charged quaternary amine moiety and can transform a neutral analyte into a charged compound by simply mixing with the analyte and allowing the mixture to stand from several minutes to 30 min at room temperature or while heating to 50 degrees C, were designed and synthesized for the highly sensitive detection of carbonyl, alcohol, carboxylic acid and primary amine samples by electrospray ionization mass spectrometry (ESI-MS). The positively charged products can be detected with high sensitivity in an ESI-MS system, which is the most popular liquid MS instrument. All of the labeled products showed a remarkably large increase in the molecular-ion peak abundance detection sensitivity of over 500-fold at picomolar concentration levels compared to that of unlabeled analytes in an ESI-MS system. These MS probes, used together with liquid MS detection, are widely applicable as a convenient method for the highly sensitive detection of less than picomolar levels of analytes, and therefore greatly enhance the power of ESI-MS analysis.     

Spectrophotometric determination of anthracycline anticancer agents with aluminum(III) and chromazurol S in a nonionic surfactant micellar medium.

A simple and highly sensitive spectrophotometric method for the determination of anthracycline anticancer agents, such as Daunorubicin hydrochloride (DAU), was established by using aluminum(III) and Chromazurol S (CAS) in a nonionic surfactant micellar medium. In the case of determination of DAU, the apparent molar absorptivity was 1.3 x 10(5) dm3 mol(-1) cm(-1) at 615 nm. Beer's law was obeyed in the concentration range of 0.028 - 2.82 microg ml(-1) for DAU. Owing to no need for solvent extraction, this method could be applied to assays of DAU and related drugs in pharmaceutical preparations.     

Characteristics of hyaluronate-hydroxyethyl acrylate blend gel and release of cationic amphiphilic solutes

Hyaluronate-hydroxyethyl acrylate blend gel (HA-PHEA) were prepared to modify the brittleness of hyaluronate gel (HA) and the characteristics of HA-PHEA gel were compared with those of HA and polyhydroxyethyl acrylate (PHEA) gels. These gels were high in water content and transparent. HA-PHEA gel was improved in viscoelastic properties due to the elasticity and the high affinity with water of PHEA, and the drying-swelling cycles became reversible. The effective charge densities theta of the gels estimated from membrane potentials were -0.002, -0.008 and 0 mol dm(-3) for HA-PHEA, HA and PHEA gels. Effects of electro- static and nonelectrostatic interactions on absorptions and releases were studied using sodium benzoate (NaBA) as an anionic solute, and methylene blue (MB), chlorpromazine (CPHCl) and benzethonium chloride (BZTCl) as cationic solutes, in which CPHCl and BZTCl are cationic amphiphilic solutes. The releases of MB, CPHCl and BZTCl from HA-PHEA and HA gels were suppressed comparing with those of NaBA. By adding salts, the releases of MB and CPHCl were enhanced but those of BZTCl were suppressed due to enhancement of the intra- and intermicelle formation. In the releases of the cationic solutes from HA-PHEA gel, electrostatic and nonelectrostatic interactions with HA were found to play important roles. Behaviors of the releases from HA-PHEA gel were found to possess the features of HA gel.     

Optical rotation inversion of porphyrin-DNA complexes

A porphyrin-DNA complex in which helical porphyrin assemblies were stacked as π-stacked aggregates on a DNA scaffold was found. The complex indicates the inversions of optical rotation by only the control of ionic equilibrium without any structural changes of DNA scaffold.     

Retention and enantioselective properties of ovomucoid-bonded silica columns Influence of physical properties of base materials and spacer length

The influence of the physical properties of base silica materials and spacer length on chiral separation of enantiomers on ovomucoid (OVM)-bonded materials was investigated. With regard to the pore size of the base silica materials, the 300-Å materials gave higher enantioselectivity, than the 120-Å materials, despite the smaller amounts of bonded OVM proteins. However, higher resolution was obtained with the latter materials. With regard to the spacer length, aminopropyl (AP)-, aminobutyl-, N-(4-aminobutyl)-3-aminopropyl- and N-(6-aminohexyl)-3-aminopropyl-silica gels were activated by N,N′-di-succinimidyl carbonate (DSC) and the proteins were bound. The first two materials showed excellent chiral resolution properties for the solutes tested, and the AP materials gave higher enantioselectivity and resolution. On the other hand, only oxprenolol enantiomers were slightly resolved on the last two materials. Also, AP-silica gels activated by DSC were compared with glycerylpropyl (GP)-silica gels activated by 1,1′-carbonyldiimidazole. The former materials gave higher resolution for acidic and basic solutes despite the lower enantioselectivity, whereas for the unchanged hexobarbital the latter materials gave higher enantioselectivity and almost equal resolution. The above results reveal that the 120-Å base silica gels are more suitable than the 300- Å base silica gels for obtaining larger amounts of bonded OVM proteins and that a less hydrophobic spacer such as an AP group and a hydrophilic spacer such as a GP group are suitable.     

Skeletal Transformation Triggered by C−F Bond Activation after Photochemical Rearrangement of Fluorinated [7]Helicenes

Tri- and tetra-fluorinated [7]helicenes are photolabile and undergo a double fluorine atom transfer. Herein, we show that the transferred product further undergoes a skeletal transformation on silica gel. The transformation begins with activation of the allylic C−F bond on the silanol surface. Then, the resulting carbocation readily undergoes a regioselective nucleophilic aromatic substitution with water, depending on the position of the fluorine substituents. Hexafluoro-2-propanol also activated the allylic C−F bond and acted as a nucleophile. These findings support the generation of a highly reactive cationic electrophilic intermediate in the successive transformations involving fluorine atoms.     

Low-temperature formation and characterization of Cu2O nanoparticles in the binary gold alloys

Thermal analyses, using differential scanning calorimetry (DSC) and dilatometry, reveal an important anomaly at low temperature for Au-25 wt.% Cu composition after homogenization at 700°C during 2 hours under vacuum followed by heating up to 160°C before water quenching. This anomaly has been already observed and not explained. Surface characterization, using scanning electron microscopy (SEM), atomic force microscopy (AFM), and scanning tunneling microscopy (STM), exhibits a specific topography, consisting of a nanostructured surface. The precipitates of nanostructured particles are homogeneously scattered all over the surface for this 18-carat gold alloy. Moreover, X-ray photoelectron spectroscopy (XPS) shows that the composition of the observed particles corresponds to cuprous oxide phase (Cu₂O). The formation of such material can be explained by the diffusion of copper atoms from the lattice to the surface at 160°C. Pulsed radio-frequency glow discharge optical emission spectroscopy (RF GD-OES) further proves the proposed Cu₂O formation through a diffusion process. The appearance of such cuprous oxide nanoparticles on the Au-Cu alloy surface explains the low-temperature DSC and dilatometry anomaly and affects directly the surface electrical resistance at low temperature. These results might open a large gate for new ideas to investigate in catalytic, electronic, and antimicrobial activities.     

Hydrochlorothiazide Enhances UVA‐Induced DNA Damage

The UVA is currently thought to be carcinogenic because, similar to UVB, it induces the formation of cyclobutane pyrimidine dimers (CPDs). Various drugs have been reported to cause photosensitive drug eruptions as an adverse effect. Although the precise mechanism of photosensitive drug eruption remains to be elucidated, it is generally accepted that free radicals and other reactive molecules generated via UV‐irradiated drugs play important roles in the pathogenesis of photosensitive drug eruptions. The waveband of concern for photo‐reactive drugs is UVA‐visible light, but some extend into the UVB region. We tested whether photosensitive drugs could enhance CPD formation after UVA exposure by using isolated DNA in the presence of several reported photosensitive drugs using high‐performance liquid chromatography. We found that the diuretic agent hydrochlorothiazide (HCT) significantly enhanced the production of TT dimers over a wide range of UVA. Furthermore, we investigated whether UVA plus HCT could enhance CPD production in xeroderma pigmentosum model mice defective in nucleotide excision repair. Immunofluorescence studies showed that CPD formation in the skin significantly increased after 365 nm narrow‐band UVA irradiation in the presence of HCT, compared with that in wild‐type mice. HCT could be used with caution because of its enhancement of UVA‐induced DNA damage.     

Synthesis of sialyl Lewis X-polysaccharide conjugates

Sialyl Lewis X (SLeX) is well known as a ligand of the cell adhesion molecule E-selectin which is specifically expressed at inflammatory lesion sites. We have synthesized several SLeX-polysaccharide conjugates and examined their potential for drug delivery to inflammatory lesions. The AUC (area under the blood concentration-time curve) 0-24 h of SLeX-CMCht (1), SLeX-CMPul (2) and SLeX-DSH (3) at the inflammatory lesion was about 60-, 300-, and 30-fold higher than that of the monovalent SLeX (7), respectively. Moreover, 1 showed 2-fold higher accumulation in the inflammatory lesion than SLN-CMCht (4), and 2 showed 2.5-fold higher accumulation than SLN-CMPul (5).