Allenyltrimethylsilylthioketenes, generated in situ through [3,3] sigmatropic rearrangement of trimethylsilylethynyl propargyl sulfides, underwent facile [4+2] cycloaddition with imines to afford the corresponding δ-thiolactams. The resulting 2-trimethylsilyl-4-methylenetetrahydroquinolidine-2-thione, obtained by the [4+2] cycloaddition using piperideine as a dienophile, was transformed into (±)-lupinine in six steps. 相似文献
In this paper, we determine the effective purity of potassium iodate as a redox standard with a certified value linked to the international system of units (SI units). Concentration measurement of sodium thiosulfate solution was performed by precise coulometric titration with electrogenerated iodine, and an assay of potassium iodate was carried out by gravimetric titration based on the reductometric factor of sodium thiosulfate assigned by coulometry. The accuracy of the coulometric titration method was evaluated by examining the current efficiency of iodine electrogeneration, stability of sodium thiosulfate solutions and dependence on the amount of sodium thiosulfate solution used. The measurement procedure for gravimetric titration of potassium iodate with sodium thiosulfate was validated based on determination of a reference material of known purity (potassium dichromate determined by coulometry with electrogenerated ferrous ions) using the same gravimetric method. Solutions of 0.2 and 0.5 mol/L sodium thiosulfate were stable over 17 days without stabilizer. Investigation of the dependency of titration results on the amount of sodium thiosulfate solution used showed no significant effects, no evidence of diffusion of the sample, and no effect of contamination appearing during the experiment. Precise coulometric titration of sodium thiosulfate achieved a relative standard deviation of less than 0.005% under repeating conditions (six measurements). For gravimetric titration, the results obtained for the effective purity of potassium dichromate were sufficiently close to its certified value to allow confirmation of the validity of the gravimetric titration was confirmed. The relative standard deviation of gravimetric titration for potassium iodate was less than 0.011% (nine measurements), and a redox standard with a certified value linked to SI units was developed. 相似文献
In this paper, we developed a microbial route to fabricate wood-inspired biomimetic composites comparable to natural wood. Focusing on the chemical composition of woody biomass, we performed in situ bioprocessing of bacterial cellulose (BC) imbibed in modified cationic lignin (Catlig), which exhibited significant bioactivity in improving the microbial growth dynamics. The structural and morphological characteristics were enhanced by the formation of hydrophobic and electrostatic interactions between BC and Catlig during biosynthesis. Microbially derived BC/Catlig composites exhibited enhanced thermal stability and crystallinity, with oriented cellulose fibers. The tensile properties, toughness, and specific strength of BC/Catlig composites were comparable to those of a heavy wood species (Zelkova serrata) under hydrated conditions and synthetic soft materials.
Biointerfaces are crucial for regulating biofunctions. An effective method of producing new biomaterials is surface modification, in particular, the hybrid organic-inorganic approach. In this paper, we propose a method for the sequential formation of hydroxyapatite and calcium carbonate on porous polyester membranes by using an improved alternate soaking process. The resulting hybrid membranes were characterized in terms of their calcium and phosphorus ion contents; further, their structure was analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), and infrared spectroscopy (IR). As a typical biofunction, protein adsorption by these hybrid membranes was investigated. Sequential hydroxyapatite and calcium carbonate formation on the membranes was successfully achieved, and the total amounts of hydroxyapatite and calcium carbonate formed were precisely regulated by the preparative conditions. The SEM and XRD characterizations were verified by comparing with the IR results. The amount of adsorbed protein correlated well with not only the amount of hydroxyapatite formed but also the combined amounts of hydroxyapatite and calcium carbonate formed. The results indicate that the hybrid membranes can function as high-performance biointerfaces that are capable of loading biomolecules such as proteins. 相似文献
As the production of engineered nanomaterials quantitatively expands, the chance that workers involved in the manufacturing
process will be exposed to nanoparticles also increases. A risk management system is needed for workplaces in the nanomaterial
industry based on the precautionary principle. One of the problems in the risk management system is difficulty of exposure
assessment. In this article, examples of exposure assessment in nanomaterial industries are reviewed with a focus on distinguishing
engineered nanomaterial particles from background nanoparticles in workplace atmosphere. An approach by JNIOSH (Japan National
Institute of Occupational Safety and Health) to quantitatively measure exposure to carbonaceous nanomaterials is also introduced.
In addition to real-time measurements and qualitative analysis by electron microscopy, quantitative chemical analysis is necessary
for quantitatively assessing exposure to nanomaterials. Chemical analysis is suitable for quantitative exposure measurement
especially at facilities with high levels of background NPs. 相似文献
We investigated the effect of fatty acids such as stearic acid (SA, 18:0), oleic acid (OA, 18:1), eicosapentaenoic acid (EPA, 20:5), and docosahexaenoic acid (DHA, 22:6) on a dipalmitoylphosphatidylcholine (DPPC) bilayer by determining the phase transition temperature, fluorescence anisotropy of 1,6-diphenyl-1,3,5-hexatriene (DPH), and detergent insolubility. Treatment with unsaturated fatty acid broadened and shifted the phase transitions of the DPPC bilayer to a lower temperature. The phase transition temperature and the value of fluorescence anisotropy of DPH at 37 degrees C decreased progressively with increasing treatment amounts of unsaturated fatty acid. A large amount of the DPPC bilayer treated with unsaturated fatty acid was dissolved in Triton X-100, obtaining a low level of detergent insolubility. These modifications of the bilayer physical properties were most pronounced with DHA and EPA treatment. These data show that unsaturated fatty acids, particularly DHA and EPA, induce a marked change in the lipid bilayer structure. The composition of fatty acids in the DPPC bilayer was similar after treatment with various unsaturated fatty acids, suggesting that the different actions of unsaturated fatty acids are attributed to change in the molecular structure (e.g., kinked conformation by double bonds). We further explored the change in physical properties induced by fatty acids dispersed in a water-in-oil-in-water multiple emulsion and found that unsaturated fatty acids acted efficiently on the DPPC bilayer, even when incorporated in emulsion form. 相似文献
The structure including the absolute configuration of a new glucoalkaloid, 3,4-dehydro-5(S)-5-carboxystrictosidine, isolated from Peruvian U?a de Gato (Cat's Claw, original plant: Uncaria tomentosa), was confirmed by synthesis starting from secologanin and L-tryptophan. 相似文献
Two new pyrrolidine alkaloids, pandamarilactonine-C and -D, were isolated from Pandanus amaryllifolius. Based on the total synthesis of pandamarilactonine-C and its related alkaloid, pandamarilactonine-A, the relative stereochemistry of pandamarilactonine-A and -B, which was previously proposed by spectroscopic analysis, was revised. 相似文献