Precise synthesis of porphyrin array scaffolding polyisocyanides

Aryl isocyanides bearing free‐base and metallo‐porphyrins were prepared and polymerized with a Pd–Pt μ‐ethynediyl complex as the initiator to give polymers with narrow polydispersity indices. The molecular weights of the resulting polymers were precisely controlled by the initial feed ratio of the porphyrin monomer to the initiator. The UV–VIS spectra suggested that the porphyrin pendants are regularly arranged to form stacked columns. Metallo‐porphyrin polymers were also prepared by reacting free‐base porphyrin polymers with metal salts. The successive reactions of free‐base and zinc‐porphyrin monomers resulted in the formation of diblock polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 585–595, 2006     

INVESTIGATIONS ON THE MECHANISM OF CHLORPROMAZINE PHOTOTOXICITY: EFFECTS ON LYSOSOMES OF CULTURED HUMAN FIBROBLASTS

Abstract The effect of chlorpromazine (CPZ) and UVA on lysosomes of cultured normal human fibroblasts has been investigated. Acid phosphatase (ACPase) activity in 12 000 g pellet of cells treated with CPZ (10 μg/m l ) and UVA (6 × 10⁴ J/m²) was found to be decreased as compared with non-treated, CPZ or UVA treated control cells. This decrease, however, was not accompanied by a concomitant increase in ACPase activity in the 12 000 g supernatant. The addition of Triton X-100 to cells pretreated with CPZ + UVA resulted in only a moderate increase in ACPase activity of the 12 000 g supernatant. ACPase activity of the cells incubated in media containing preirradiated CPZ was also found to he decreased. These results indicate that CPZ + UVA directly inactivate lysosomal enzymes, possibly without affecting the membrane.     

THE ACTION SPECTRUM AND DOSE RESPONSE STUDIES OF UNSCHEDULED DNA SYNTHESIS IN NORMAL HUMAN FIBROBLASTS

Abstract— Excision repair of DNA damage by UV has been assessed in normal human fibroblasts in culture by measuring unscheduled DNA synthesis. Dose response experiments indicated that the same chromophore was involved in UV-induced damage and excision repair at three different wavelengths between 260 and 300 nm. Action spectra for unscheduled DNA synthesis were determined at wavelengths between 260 and 320 nm 30 min after irradiation using 2 doses of UV, 100 J m^-2and 10Jm^-2. Experiments at the lower dose were carried out because it appeared that repair was saturated with the higher dose at 260 and 280 nm. To explore this part of the spectrum further, experiments were performed with different doses at 260 and 280 nm and unscheduled DNA synthesis assessed 30 min and 24 h after irradiation. At 24 hr after irradiation a significantly greater amount of unscheduled DNA synthesis occurred at 280 nm. It is suggested, therefore, that both DNA and protein are concerned in the absorption of UV which leads to DNA damage and excision repair.     

Changes in Hip and Knee Muscle Strength in Patients Following Total Hip Arthroplasty

Objective: To investigate changes in hip and knee muscle strength in patients before and after total hip arthroplasty (THA) in comparison with that in healthy adults. Methods: The study included 21 women who underwent unilateral THA (THA group) and 21 age-matched healthy women (healthy group). Maximal isometric strengths of hip flexors, extensors, and abductors, and knee extensors and flexors were measured before surgery and at 4 weeks and 6 months after surgery. Results: Before surgery, muscle strength on both sides, except for hip flexors on the uninvolved side, was significantly lower in the THA group than the corresponding muscle strength in the healthy group. Up to 6 months after THA, strength of all muscle groups on both sides was significantly improved compared with their preoperative status, although the knee extensor strength on the involved side temporarily worsened at 4 weeks. However, the strength of hip extensors and knee extensors on the involved side, and hip abductors on both sides in the THA group remained below that in the healthy group. Conclusions: Our results suggest that rehabilitation specialists should consider increasing the focus on the uninvolved side and encourage patients to continue strength training beyond 6 months after surgery.     

Crystalline‐Sponge‐Based Structural Analysis of Crude Natural Product Extracts

Characterization of complex natural product mixtures to the absolute structural level of their components often requires significant amounts of starting materials and lengthy purification process, followed by arduous structure elucidation efforts. The crystalline sponge (CS) method has demonstrated utility in the absolute structure elucidation of isolated organic compounds at miniscule quantities compared to conventional methods. In this work, we developed a new CS‐based workflow that greatly expedites the in‐depth structural analysis of crude natural product extracts. Using a crude extract of the red alga Laurencia pacifica, we showed that CS affinity screening prior to compound isolation enables prioritization of analytes present in the extract, and we subsequently resolved the molecular structures of six sesquiterpenes with stereochemical clarity from around 10 mg crude extract. This study demonstrates a new chemotyping workflow that can greatly accelerate natural product discovery from complex samples.     

Synthesis of conjugated oligomers having aromatic and enediyne units alternately in the backbone that show intense fluorescence emission

[structure: see text] Synthesis and fluorescence properties of pi-conjugated compounds having alternately an aromatic ring such as benzene, pyridine, and thiophene and an enediyne unit in the backbone are described.     

Strong and selective binding of amiloride to an abasic site in RNA duplexes: thermodynamic characterization and microRNA detection

Firmly tied: The binding affinity of amiloride for an abasic (AP) site-containing RNA duplex is two orders of magnitude superior to the affinity of the corresponding AP site-containing DNA duplex. The observed high binding affinity for the RNA duplex arises from a favorable enthalpy gain. The binding-induced fluorescence response of amiloride is applicable to microRNA detection.     

Physicochemical characterization of tamoxifen citrate pseudopolymorphs, methanolate and ethanolate

Two novel pseudopolymorphs, methanolate and ethanolate of tamoxifen [(Z)-2-[4-(1,2-diphenyl-1-butenyl)phenoxy]-N,N-dimethylethylamine]citrate, were prepared in addition to forms A and B reported previously. Their crystalline forms were identified and characterized by powder and single crystal X-ray diffractometry, differential scanning calorimetry, thermogravimetric analysis, hot-stage microscopy, scanning electron microscopy and diffuse reflectance infrared Fourier-transform spectroscopy, and their physicochemical stability was also evaluated. The results of single crystal X-ray analysis and thermogravimetric analysis of methanolate and ethanolate suggested that the stoichiometry of tamoxifen citrate : methanol and tamoxifen citrate : ethanol could be composed of a 1 : 1 molecular ratio for both solvates. The results of physicochemical stability evaluations at 75 and 97% RH at 40 and 60 degrees C indicated that the metastable form A was quite stable for at least 2 months even under severe storage conditions, whereas methanolate immediately transformed to a crystalline mixture of forms A and B, and subsequently changed to the stable form B.