The transformation of α-aminoacids into fluoroacids

The reactions of some α-aminoacids with excess sodium nitrite in polyhydrogen fluoride-pyridine are described.     

Electron Microscopy of Rhamnolipid (Biosurfactant) Morphology: Effects of pH, Cadmium, and Octadecane

A rhamnolipid biosurfactant produced by Pseudomonas aeruginosa ATCC 9027 is reported to increase the aqueous dispersion and biodegradation of petroleum hydrocarbons and to complex heavy metals. These reports indicate the potential for application of rhamnolipids in remediation of contaminated sites. Effective use of rhamnolipids will require understanding of rhamnolipid morphology and the effects of pH and organic and inorganic contaminants on that morphology. We used cryo-transmission electron microscopy to investigate the morphology of vitrified, frozen hydrated suspensions of rhamnolipid over a pH range of 5.5 to 8.0, and to determine the effect of a model alkane, octadecane, and a model heavy metal, cadmium, on rhamnolipid morphology. Micrographs clearly showed that rhamnolipid morphology was a function of pH, changing from lamellar, to vesicular, to micellar as pH increased. The effect of cadmium and octadecane on rhamnolipid morphology was determined at pH 6.8 and 7.0, where maximum cadmium complexation and maximum octadecane dispersion occurs. Cadmium seemed to stabilize rhamnolipid vesicle structures as shown by an increase in vesicle number and a decrease in vesicle diameter. In contrast, octadecane favored the micellar structure as shown by the complete absence of vesicles.     

Chemical and antifungal properties of the copper(II) complexes of 2-formylpyridine4 N-methyl-,4 N-dimethyl,4 N-diethyl and4 N-dipropylthiosemicarbazones

Summary Two series of copper(II) complexes. [Cu(HL)X₂] and [Cu(L)Cl], where HL is a 2-formylpyridine⁴ N-substituted thiosemicarbazone, L is an anion formed by loss of the²N hydrogen and X=Cl or Br, have been prepared and spectrally characterised. Their growth inhibition ofAspergillus niger andPaecilomyces variotii has been measured and compared with analogous complexes formed from 2-acetylpyridine thiosemicarbazones.     

The preparation and reduction of 5-cyano-3-indolylketones. Synthesis of 5-cyanotryptamines

The acylation of indoles under acidic conditions has been studied. Stannic chloride was shown to be an effective catalyst for the preparation of some 3-acylindoles, notably 5-cyano-3-indolylketones. The various 5-cyano -3 - indolylketones were reduced with sodium borohydride to yield either the 5-cyano-3-carbinols or 5-cyano-3-alkylindoles. 5-Cyanotryptamines were obtained by reduction of appropriate α-dialkylamino and α-azidoketones. A cleavage reaction of the carbinols involving loss of the 3-side chain to yield 5-cyanoindole is also described.     

Nanoscale patterning of alkyl monolayers on silicon using the atomic force microscope

Self-assembled monolayers (SAMs) of 1-alkenes on hydrogen-passivated silicon substrates were successfully patterned on the nanometer scale using an atomic force microscope (AFM) probe tip. Nanoshaving experiments on alkyl monolayers formed on H-Si(111) not only demonstrate the flexibility of this technique but also show that patterning with an AFM probe is a viable method for creating well-defined, nanoscale features in a monolayer matrix in a reproducible and controlled manner. Features of varying depths (2-15 nm) were created in the alkyl monolayers by controlling the applied load and the number of etching scans made at high applied loads. The patterning on these SAM films is compared with the patterning of alkyl siloxane monolayers on silicon and mica.     

THE ROLE OF UROCANIC ACID IN UV-INDUCED IMMUNOSUPPRESSION: RECENT ADVANCES (1992–1994)

Abstract— Cis - urocanic acid (UCA), formed in the epidermis by UV irradiation of trans-UCA , has been implicated as a mediator of the immunosuppression induced by UV exposure of the skin. This review covers recent work in which the wavelength dependence of cis-UCA formation, the interaction of UCA isomers with DNA, the effects of UCA isomers on the immune system and their interaction with histamine are examined. Results are frequently conflicting, particularly when considering the possible mode of action of cis -UCA but, overall, a multifaceted role for UCA in immunomodulation by UV radiation is substantiated.     

Measured solar ultraviolet radiation exposures of outdoor workers in Queensland in the building and construction industry

The risk to outdoor workers of exposure to solar ultraviolet radiation (UVR) has been known for some time, particularly in the building and construction industry, where workers often use little in the way of protection against solar UVR. In recent years there have been attempts by authorities in Australia and in Queensland in particular, where UVR levels in spring and summer are very high to extreme, to instigate and to encourage the use of personal UVR protection by outdoor workers. To quantify UVR exposure of building and construction industry workers involved in typical outdoor work, a study was conducted using UVR-sensitive polysulphone film badges. The results indicated that the doses were significant, often well in excess of recommended exposure limits. The measured exposures varied between trades. Data on the use of personal UVR-protective equipment and the skin type of workers were also collected. Many of the workers had skin types that were sensitive to UVR and showed signs of sunburn. In summary, the study found that at-risk individuals were exposed to extreme levels of UVR, in most cases without adequate and appropriate sun protection.     

Preclinical studies in normal canine prostate of a novel palladium-bacteriopheophorbide (WST09) photosensitizer for photodynamic therapy of prostate cancers

Photodynamic therapy (PDT) uses light to activate a photosensitizer to achieve localized tumor control. In this study, PDT mediated by a second-generation photosensitizer, palladium-bacteriopheophorbide WST09 (Tookad) was investigated as an alternative therapy for prostate cancer. Normal canine prostate was used as the animal model. PDT was performed by irradiating the surgically exposed prostate superficially or interstitially at 763 nm to different total fluences (100 or 200 J/cm2; 50, 100 or 200 J/cm) at 5 or 15 min after intravenous administration of the drug (2 mg/kg). Areas on the bladder and colon were also irradiated. The local light fluence rate and temperature were monitored by interstitial probes in the prostate. All animals recovered well, without urethral complications. During the 1 week to 3 month post-treatment period, the prostates were harvested for histopathological examination. The PDT-induced lesions showed uniform hemorrhagic necrosis and atrophy, were well delineated from the adjacent normal tissue and increased linearly in diameter with the logarithm of the delivered light fluence. A maximum PDT-induced lesion size of over 3 cm diameter could be achieved with a single interstitial treatment. There was no damage to the bladder or rectum caused by scattered light from the prostate. The bladder and rectum were also directly irradiated with PDT. At 80 J/cm2, a full-depth necrosis was observed but resulted in no perforation. At 40 J/cm2, PDT produced minimal damage to the bladder or rectum. On the basis of optical dosimetry, we have estimated that 20 J/cm2 is the fluence required to produce prostatic necrosis. Thus, the normal structure adjacent to the prostate can be safely preserved with careful dosimetry. At therapeutic PDT levels, there was no structural or functional urethral damage even when the urethra was within the treated region. Hence, Tookad-PDT appears to be a promising candidate for prostate ablation in patients with recurrent, or possibly even primary, prostate cancer.     

Matrix‐assisted laser desorption/ionization time‐of‐flight analysis of the copolymerization reaction of an expanding monomer with a diepoxide

In search of a composite with low stress and low shrinkage properties, this study includes matrix‐assisted laser desorption/ionization time‐of‐flight analysis of the photoinitiated cationic polymerization between an expanding monomer [1,5,7,11‐tetraoxaspiro[5.5]undecane (TOSU)] and a diepoxide [bisphenol A diglycidyl ether (BADGE)]. Past studies using NMR and differential scanning calorimetry analyses concluded copolymerization indirectly on the basis of deviations from homopolymer product data. This is the first study to provide direct evidence of copolymerization between these species. Unlike previous research, this study enables the identification of the TOSU homopolymer and the absence of the BADGE homopolymer, suggesting initial cationic activation of TOSU. In addition to peaks that correspond to the presumed mechanism for six‐membered TOSU polymerization, many peaks have a net gain or loss of cyclic carbonate in support of a new polymerization mechanism participating in the reaction. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5962–5970, 2005     

Azobenzene on Cu(110): adsorption site-dependent diffusion

Azobenzene and its derivatives can undergo reversible trans-cis isomerizations when irradiated with light, making them potential candidates for optically sensitive materials and devices. The adsorption and diffusion of azobenzene on the Cu(110) surface was investigated with a variable-temperature scanning tunneling microscope. The trans-isomer was observed and found to occupy two adsorption geometries-an energetically stable and a metastable state. Diffusion occurred along the closed-packed [1 -1 0] direction of the surface, and the diffusivity for the two adsorption states was found to differ by approximately 1 order of magnitude.