Thioridazine induces immediate and delayed erythema in photopatch test

Thioridazine is a phenothiazine derivative that has been used as an antipsychotic; it rarely causes photosensitization. However, we noticed that this drug induced an erythematous reaction in a photopatch test. Six volunteers were patch tested with various concentrations of thioridazine and irradiated with a range of UVA doses, and the time courses of the color of and blood flow to the test sites were monitored. The free-radical metabolites of thioridazine generated under UVA irradiation and its effects on ascorbate radical formation were examined with an electron paramagnetic resonance (EPR) spectrometer in vitro. As a result, immediate erythema developed during UVA irradiation in most subjects when 1% thioridazine was applied for 48 h and irradiation doses were higher than 4 J cm(-2). Another peak of erythematous reaction was observed 8-12 h after irradiation. The in vitro examination detected an apparent EPR signal, which appeared when 2 mM thioridazine in air-saturated phosphate buffer was irradiated with UVA, whereas this reaction was attenuated under anaerobic conditions. The EPR signal of the ascorbate radical was augmented under both aerobic and anaerobic conditions. Thioridazine-derived oxidants and/or thioridazine radicals generated during UVA irradiation seem to play an important role in this unique phototoxic reaction.     

Physicochemical properties of artificial proteins that accelerate nucleation of crystalline calcium phosphate

We have created 18 artificial proteins by embedding two calcification motifs found in a protein involved in bone and dentin formation. The relationship between the physicochemical properties of the proteins and their in vitro mineralization activities was investigated. Two slightly acidic proteins nucleated octacalcium phosphate (OCP) at a low protein concentration from a solution where precipitation did not occur without the proteins. Among 16 basic proteins, only one protein nucleated OCP at the same protein concentration. At a higher protein concentration, four proteins self-assembled to become large aggregates, and these four proteins nucleated OCP. Among 14 proteins without the self-assembling property, only five proteins nucleated OCP. None of the proteins formed α-helix or ß-sheet structures. These results suggest that the proteins that had the self-assembling property appeared to exhibit nucleation activity with high frequency and that the formation of the ordered backbone conformation was not required for proteins to promote nucleation.     

Green-light-driven thioxanthylium-based organophotoredox catalysts: Organophotoredox promoted radical cation Diels-Alder reaction

Thioxanthylium-based organophotoredox catalysts that operate under irradiation with green light have been developed. These catalysts present high excited-state reduction potentials (E₀′(C¹/C^?)?=?+1.79–1.94?V vs SCE). They are able to efficiently activate dienophiles under green or blue light irradiation afforded the targeted radical cation Diels-Alder cycloadducts in good yields. The present thioxanthylium-based catalysts provide a new green-light-driven photoredox catalysis system.     

Extraction of hidden information of ToF‐SIMS data using different multivariate analyses

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) is a powerful tool for determining surface information of complex systems such as polymers and biological materials. However, the interpretation of ToF‐SIMS raw data is often difficult. Multivariate analysis has become effective methods for the interpretation of ToF‐SIMS data. Some of multivariate analysis methods such as principal component analysis and multivariate curve resolution are useful for simplifying ToF‐SIMS data consisting of many components to that explained by a smaller number of components. In this study, the ToF‐SIMS data of four layers of three polymers was analyzed using these analysis methods. The information acquired by using each method was compared in terms of the spatial distribution of the polymers and identification. Moreover, in order to investigate the influence of surface contamination, the ToF‐SIMS data before and after Ar cluster ion beam sputtering was compared. As a result, materials in the sample of multiple components, including unknown contaminants, were distinguished. Copyright © 2014 John Wiley & Sons, Ltd.     

Degradation of aliphatic and aliphatic–aromatic co-polyesters by depolymerases from Roseateles depolymerans strain TB-87 and analysis of degradation products by LC-MS

The degradation activities of bacterium, Roseateles depolymerans TB-87 and its depolymerases Est-H and Est-L against aliphatic as well as aliphatic–aromatic co-polyesters, were investigated. Strain TB-87 and its enzymes exhibited an ability to degrade aliphatic and aliphatic–aromatic co-polyesters. Monomers produced as a result of degradation of aliphatic polyesters [poly(butylene succinate) (PBS), poly(butylene succinate-co-adipate) (PBSA)] as well as aliphatic–aromatic co-polyester [poly(butylene succinate/terephthalate/isophthalate)-co-(lactate) (PBSTIL) by depolymerases Est-H and Est-L were investigated by liquid chromatography mass-spectrometry (LC-MS). Some common monomers like succinic acid and 1,4-butanediol were detected besides adipic acid and terephthalic/isophthalic acids as degradation products from PBSA and PBSTIL, respectively, whereas lactic acid was not detected. The succinic acid monomer was detected prior to adipic acid as a result of degradation of PBSA. The enzymes depolymerized PBS also into respective monomers. The analysis of PBSTIL degradation products revealed that enzymes easily degraded aliphatic segments as compared to aromatic segments and resulted in production of succinic acid prior to terephthalic and isophthalic acid. On the basis of these results, we speculate that both the enzymes Est-H and Est-L, attacked succinic acid segments (BS) first instead of adipic acid (BA) and terephthalic/isophthalic acid (BT or BI) segments of PBSA and PBSTIL, respectively. It is concluded from the results that R. depolymerans strain TB-87 can depolymerize aliphatic as well as aliphatic–aromatic co-polyesters; therefore, its enzymes can be applied in the process of biochemical monomer recycling.     

A new Kdo derivative for the synthesis of an inner-core disaccharide of lipopolysaccharides and lopooligosaccharides

Methyl (7,8-di-O-benzoyl-4,5-O-isopropylidene-3-deoxy-d-manno-2-oct-ulopyranoside)onate was found to be a useful new intermediate in the synthesis of an inner-core oligosaccharide of lipooligosaccharides and lipopolysaccharides produced by gram-negative bacteria. This intermediate could be converted to the corresponding glycosyl fluoride and 4,5-diol acceptor with ease. Syntheses of dimeric Kdo, O-(sodium 3-deoxy-α-d-manno-2-octuropyranosylonate)-(2-4)-sodium (allyl 3-deoxy-α-d-manno-2-octuropyranoside)onate, and O-(sodium 3-deoxy-α-d-manno-2-octuropyranosylonate)-(2-8)-sodium (allyl 3-deoxy-α-d-manno-2-octuropyranoside)onate were successfully demonstrated.     

Discovery of novel Thieno[2,3-d]pyrimidin-4-yl hydrazone-based cyclin-dependent kinase 4 inhibitors: synthesis, biological evaluation and structure-activity relationships

The design, synthesis, and evaluation of novel thieno[2,3-d]pyrimidin-4-yl hydrazone analogues as cyclin-dependent kinase 4 (CDK4) inhibitors are described. In continuing our program aim to search for potent CDK4 inhibitors, the introduction of a thiazole group at the hydrazone part has led to marked enhancement of chemical stability. Furthermore, by focusing on the optimization at the C-4' position of the thiazole ring and the C-6 position of the thieno[2,3-d]pyrimidine moiety, compound 35 has been identified with efficacy in a xenograft model of HCT116 cells. In this paper, the potency, selectivity profile, and structure-activity relationships of our synthetic compounds are discussed.     

Deprotonation Processes of Ellagic Acid in Solution and Solid States

Monatshefte für Chemie - Chemical Monthly - ?The electronic absorption and polarized absorption spectra were measured at various pH conditions for ellagic acid. Comparison of these...     

Near-Infrared Spectroscopy Probe with Position Sensor

We propose a probe for near-infrared spectroscopy that enables exploratory diagnosis and the simultaneous measurement of metabolic status and dynaMisc of the body of a subject. The probe has a red light emitting diode for indicating its position in addition to a set of two near-infrared light emitting diodes and a photodetector for near-infrared spectroscopy measurement. The red light is detected by a camera and the probe position is obtained by processing the captured images. There are two methods of using the probe: In one method, the user scans the probe on the body surface to obtain a spatial distribution of metabolic status; in the other method, the probe is fixed on the body and simultaneously measures metabolic status and movement of the body to investigate their relationship.