Radical cyclization of sugar-derived beta-(alkynyloxy)acrylates: synthesis of novel fused ethers

[formula: see text] Tributyltin radical mediated cyclization of carbohydrate-derived beta-(alkynyloxy)acrylates leading to highly functionalized cis- and trans-fused bicyclic ethers of various ring sizes is described. The efficacy of the radical cyclization is nicely illustrated in the iterative construction of a trans-fused tricyclic tetrahydropyran.     

New information on water interfacial structure revealed by phase-sensitive surface spectroscopy

A phase-sensitive sum-frequency vibrational spectroscopic technique is developed to study interfacial water structure of water/quartz interfaces. Measurements allow deduction of both real and imaginary parts of the surface nonlinear spectral response, revealing an unprecedentedly detailed picture of the net polar orientations of the water species at the interface. The orientations of the icelike and liquidlike species appear to respond very differently to the bulk pH change indicating the existence of different surface sites on quartz with different deprotonation pK values.     

Surface complexation studied via combined grazing-incidence EXAFS and surface diffraction: arsenate on hematite (0001) and (10-12)

X-ray diffraction [crystal-truncation-rod (CTR)] studies of the surface structure of moisture-equilibrated hematite reveal sites for complexation not present on the bulk oxygen-terminated surface, and impose constraints on the types of inner-sphere sorption topologies. We have used this improved model of the hematite surface to analyze grazing-incidence EXAFS results for arsenate sorption on the c (0001) and r (10–12) surfaces measured in two electric vector polarizations. This work shows that the reconfiguration of the surface under moist conditions is responsible for an increased adsorption density of arsenate complexes on the (0001) surface relative to predicted ideal termination, and an abundance of “edge-sharing” bidentate complexes on both studied surfaces. We consider possible limitations on combining the methods due to differing surface sensitivities, and discuss further analysis possibilities using both methods. An erratum to this article can be found at     

ICP-AES法测定内蒙古地区六种沙生木本植物中金属元素

采用ICP-AES法分别对内蒙古地区梭梭、小叶锦鸡儿、沙冬青、红柳、沙枣和沙柳等六种沙生木本植物中金属元素进行了测定和分析。该方法的加标回收率为94.98％～120.25％,RSD＜3.4％,具有良好的准确度和精密度。结果表明,常量元素Ca,K,Mg,Na,Al及植物生命活动所必需的微量元素Fe,Mn,Cu,Zn在六种沙生木本植物中表现为不同的含量顺序,且Fe,Mn,Cu,Zn四种元素的含量均低于陆生高等植物的平均含量。该测定结果为改善西部地区生态环境,选择优良防风固沙树种提供可靠的数据和理论依据。     

An effective synthesis method for secondary fluorinated alcohols via the reaction of esters of polyfluorinated acids with trialkylalanes

Unlike nonfluorinated analogs, complex esters of polyfluorinated acids in reactions with trialkylalanes produce only polyfluorinated secondary alcohols.Department of Fine Organic Synthesis, Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences, 450054 Ufa. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2339–2341, October, 1992.     

Analysis and simulation of the structure of nanoparticles that undergo a surface-driven structural transformation

A room temperature solid-state structural transformation was observed in 3 nm ZnS nanoparticles in methanol following the addition of water (Zhang et al., Nature 424, 1025, 2003). Experimental wide angle x-ray scattering (WAXS), x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) spectroscopy measurements show a large increase in crystallinity associated with water addition, in agreement with molecular dynamics (MD) predictions. Here we perform first-shell EXAFS and pair distribution function analysis and whole-nanoparticle calculations of WAXS, EXAFS and XANES to compare structural data with the MD predictions. The predicted WAXS patterns give excellent agreement with data, while the predicted EXAFS and XANES spectra give poor agreement. Relative to WAXS, XANES and EXAFS spectra contain additional structural information related to the distribution of disorder. The discrepancy between the x-ray diffraction and x-ray absorption results indicates that structural disorder is partitioned between interior and surface regions more strongly than predicted in the MD simulations.     

The interfacial structure of water/protonated α-Al2O3 (11 ?20) as a function of pH

Sum frequency vibrational spectroscopy (SFVS) was used to study the structure of the protonated α-Al(2)O(3) (11 ?20), and water/α-Al(2)O(3) (11 ?20) interfaces as a function of pH. By combining SFVS spectra with an oxygen-terminated model suggested by x-ray reflectivity, we are able to understand several details of the protonated α-Al(2)O(3) (11 ?20) interface structure. For example, the spectral changes observed for the water/α-Al(2)O(3) (11 ?20) interface with varying pH could be accounted for by the protonation/deprotonation of particular surface hydroxyls. Our spectra also indicate that the point of zero charge for this interface is at pH ~ 6.7.     

雾化角对液体火箭发动机燃烧室压力振荡的影响

针对液氧/煤油火箭发动机模型燃烧室实现了三维非稳态两相燃烧过程的数值模拟,得到的燃烧室截面平均压力和平均速度与实验吻合。在初边值条件不施加任何扰动的情况下,得到了燃烧室压力自激振荡过程,并研究了液氧和煤油喷嘴雾化角对燃烧室压力振荡的影响。计算结果表明:当雾化角为40°或120°时,由于燃料与氧化剂喷雾锥重叠区域较小或较大,导致了推进剂混合很差或很好,不易在燃烧室头部出现局部爆炸性的可燃混气团,致使燃烧室压力振荡强度较弱;而当雾化角为中间值65°时,易于出现爆炸性的可燃气团并导致剧烈的压力振荡,使燃烧室中出现燃烧不稳定性。因此,雾化角的合理设计是抑制燃烧不稳定性的一种途径。