Effects of aldehyde or dipyrromethane substituents on the reaction course leading to meso-substituted porphyrins

To better understand the effects of diverse substituents on reactions leading to porphyrins, pyrrole+aldehyde condensations and related reactions of dipyrromethanes were examined. The course of pyrrole+aldehyde condensations was investigated by monitoring the yield of porphyrin (by UV-Vis spectroscopy), reaction of aldehyde (by TLC), and changes in the composition of oligomers (by laser desorption mass spectrometry). Reaction reversibility was examined via exchange experiments. Reversibility of reactions leading to porphyrin was further probed with studies of dipyrromethanes. The reaction course was found to depend on the nature of the substituent and the acid catalyst. Alkyl or electron-donating substituents displayed levels of reversibility (exchange/scrambling) on par or greater than that of the phenyl substituent, whereas electron-withdrawing or sterically bulky substituents exhibited little to no reversibility. The results obtained provide insight into the electronic and steric effects of different substituents and should facilitate the design of synthetic plans for preparing porphyrinic macrocycles.     

Cavitation mechanism in cyanobacterial growth inhibition by ultrasonic irradiation

To prevent cyanobacterial bloom in eutrophic water by ultrasonic method, ultrasonic irradiations with different parameters were tested to inhibit Spirulina platensis from growth. The experimental result based on cyanobacterial growth, chlorophyll a and photosynthetic activity showed that, the ultrasonic irradiation inhibited cyanobacterial proliferation effectively, furthermore the inhibition effectiveness increased in the order: 200 kHz>1.7 MHz>20 kHz and became saturated with the increased power. The inhibition mechanism can be mainly attributed to the mechanical damage to the cell structures caused by ultrasonic cavitation, which was confirmed by light microscopy and differential interference microscopy. The optimal frequency of 200 kHz in cavition and sonochemistry was also most effective in cyanobacterial growth inhibition. The higher frequency of 1.7 MHz is weaker than 20 kHz in cavitation, but has more effective inhibition because it is nearer to the resonance frequency of gas vesicle. The inhibition saturation with ultrasonic power was due to the ultrasonic attenuation induced by the acoustic shielding of bubbles enclosing the radiate surface of transducer.     

Deformation of styrene—divinylbenzene copolymers and hypercrosslinked polystyrenes during solvent adsorption and desorption

An automated procedure was developed for monitoring fast changes in the size of spherical samples of polymers during their contact with a solvent or drying. The kinetics of bulk deformation in these processes was studied for a series of cross-linked polymers, viz., gel-type and porous styrene—divinylbenzene copolymers and poly(divinylbenzenes), and hypercrosslinked polystyrenes. Gel, macroporous, and hypercrosslinked polystyrenes are substantially different in the rate, mechanism, and degree of swelling, which is associated with the principal differences in their physical structures. An unusual effect of a sharp decrease followed by a temporary increase in the volume of porous polystyrene and poly(divinylbenzene) materials were observed during desorption (evaporation) of organic solvents. Water desorption is accompanied by an excessive bulk compression of porous granules giving rise to negative deformations, which gradually relax to the state equilibrium for the dry polymer. The results of dynamic desorption porometry (for water desorption) are indicative of a bimodal size distribution of micropores in hypercrosslinked polystyrene. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 467–476, March, 2007.     

Electron-stimulated desorption of D (H) from condensed D2O (H2O) films

The electron-stimulated desorption (ESD) of D⁻ and H⁻ ions from condensed D₂O and H₂O films is investigated. Three low-energy peaks are observed in the ESD anion yield, which are identified as arising from excitation of ²B₁, ²A₁ and ²B₂ dissociative electron attachment (DEA) resonances. Additional structure is observed between 18 and 32 eV, which may be due to ion pair formation or to DEA resonances involving the 2a₁ orbital. The ion yield resulting from excitation of the ²B₁ resonance increases as the film is heated. We attribute the increase in the ion yield to thermally induced hydrogen bond breaking near the surface, which enhances the lifetimes of the excited states that lead to desorption.     

An efficient calculation algorithm for focusing by plane ultrasonic transducers

In the present paper, we simulate focused wave fields generated by a system of plane transducers used in an immersion ultrasonic technique. The ultrasonic beam penetrates into the elastic medium through the fluid-solid boundary. A real-time computer algorithm is proposed to calculate stress components in the solid medium. It is shown that a good focusing wave structure can be provided by a pair of plane rectangular transducers, inclined with respect to each other and to the beam acoustic axis.     

Au deposits on graphite: On the nature of high temperature desorption peaks in CO thermal desorption spectra

Due to the discovery of Au as a catalyst for low temperature CO oxidation, the adsorption of CO on Au surfaces has attracted a lot of attention recently. On stepped and rough single crystal surfaces as well as on deposited particles two characteristic desorption states above 100 K have been observed via TPD. We have studied Au deposits on graphite in order to elucidate the nature of these desorption peaks in more detail. For this purpose, Au was deposited at 100 K and 300 K on HOPG as a weakly interacting support. In analogy to other supports, we obtain two desorption states (∼140 K and ∼170 K) whose relative intensities depend strongly on the deposition temperature with the high temperature peak being much more pronounced for the 100 K deposits. After annealing to 600 K, both states drastically lose intensity. XP spectra, on the other hand, show virtually no decrease of the Au 4f intensity as would be expected for desorption or significant changes of the particle morphologies. We conclude that both desorption peaks are defect-related and connected with under-coordinated Au atoms that are lost for the most part upon annealing. These sites could be located at the perimeter of dendritic islands or on small, defect-rich particles in addition to larger particles not adsorbing CO at 100 K. Preliminary STM results are in favour of the second interpretation.     

亲和标记-基质辅助激光解吸电离飞行时间质谱用于蛋白质相对定量方法的研究

将亲和标记技术和基质辅助激光解吸电离飞行时间串联质谱联用,建立了蛋白质相对定量方法,以牛血清白蛋白为实验对象,考察了该方法的准确度、重现性等指标;又以数种标准蛋白混合物为研究对象,考察了该方法的动态范围及相应的标准偏差,为实际生物样品中差异蛋白质分析奠定了基础。