Spherical Particles of Zirconia-Titania of Hexagonal Structure from a Neutral Amine Route

Through the sol–gel process, using the so-called neutral amine route, spherical particles of 1:1 zirconia–titania were synthesized from zirconium(IV) and titanium(IV) butoxides as well as 1,12-diaminododecane as precursor species. The obtained product exhibited a hexagonal structure, as determinated by X-ray diffraction data. The obtained material was also characterized by thermogravimetry, differential scanning calorimetry, infrared spectroscopy, scanning electron microscopy, and surface area measurements. Despite the release of template molecules on heating, the spherical morphology was retained up to about 1200°C, at which the disruption of the spheres took place.     

Effects of Adsorbed Polyaniline on Redox Process on MoO3 Surface

The effects exhibited by adsorbed conducting polyaniline on the redox process on a molybdenum oxide surface were studied. Thermogravimetric results indicate a 4% polyaniline deposition. Cyclic voltammograms of the adsorbed polymer on MoO3 show that polyaniline exerts remarkable effects on the molybdenum blue oxidation-reduction process, with oxidation and reduction potentials of 0.33 and 0.18 V, respectively. This effect strongly enhances the electrode response, and can be used as an important tool in qualitative and/or quantitative determinations of molybdenum in solution as well as in any substrate. Copyright 1999 Academic Press.     

Native chemical ligation of thioamide-containing peptides: development and application to the synthesis of labeled α-synuclein for misfolding studies

Thioamide modifications of the peptide backbone are used to perturb secondary structure, to inhibit proteolysis, as photoswitches, and as spectroscopic labels. Thus far, their incorporation has been confined to single peptides synthesized on solid phase. We have generated thioamides in C-terminal thioesters or N-terminal Cys fragments and examined their compatibility with native chemical ligation conditions. Most sequence variants can be coupled in good yields with either TCEP or DTT as the reductant, though some byproducts are observed with prolonged TCEP incubations. Furthermore, we find that thioamides are compatible with thiazolidine protection of an N-terminal Cys, so that multiple ligations can be used to construct larger proteins. Since the acid-lability of the thioamide prohibits on-resin thioester synthesis using Boc chemistry, we devised a method for the synthesis of thioamide peptides with a masked C-terminal thioester that is revealed in situ. Finally, we have shown that thioamidous peptides can be coupled to expressed protein fragments to generate large proteins with backbone thioamide labels by synthesizing labeled versions of the amyloid protein α-synuclein for protein folding studies. In a proof-of-principle experiment, we demonstrated that quenching of fluorescence by thioamides can be used to track conformational changes during aggregation of labeled α-synuclein.     

Novel Ortho effects detected in the fast atom bombardment mass spectra of substituted bisaryl phosphate antagonists of platelet-activating factor

A series of substituted bisaryl phosphate compounds, (R¹CH₂)⁺ ArOP = O(O^?)(OArR²R₃), was analyzed and characterized by fast atom bombardment mass spectrometry. Abundant fragment ions were observed and correlated with the proposed structures. From fragmentation pattersn, ‘ortho effect’ reactions were demonstrated to have occurred when the phosphoryl oxygen reacted with the (CH₂R¹)⁺ and C?O(OCH₃) substituents in the ortho position, relative to the phosphate group, and displaced the R¹ and OCH₃ groups, respectively, to produce phosphorus containing six-membered rings fused to the aryl moiety. When the (CH₂R¹)⁺ substituents were in the meta position relative to the phosphate group, the ‘ortho effect’ reactions were not observed. However, when the C?O(OCH₃) substituent was in the meta position relative to the phosphate group, an abundant fragment ion containing a five-membered phosphate ring fused to the aryl ring was detected with the original phosphoryl oxygen ortho to both the phosphate oxygen and a formyl group, formed from the original C?O(OCH₃) substituent. All other fragmentations not involving the ‘ortho effect’ reactions were nearly identical for the different structural isomers of the substituted bisaryl phosphate compounds.     

Thioamide quenching of intrinsic protein fluorescence

Thioamides quench tryptophan and tyrosine fluorescence in a distance-dependent manner and thus can be used to monitor the binding of thioamide-containing peptides to proteins. Since thioamide analogs of the natural amino acids can be synthetically incorporated into peptides, they can function as minimally-perturbing probes of protein/peptide interactions.     

HL-2M 装置电子回旋共振加热及电流驱动系统设计与研制进展

根据 HL-2M 装置物理实验加热的需求,完成了总功率为 8MW 的电子回旋共振加热及电流驱动 (ECRH/ECCD)系统设计,开展了波源、传输及天线等关键部件研制。8MW ECRH/ECCD 系统,由 8 套 105GHz/  1MW/3s 波源系统、8 条内径为 63.5mm 的真空传输线及三套极向实时可控的发射天线构成。目前,已完成 ECRH/ECCD 系统关键部件研制及其相关的桌面与高功率性能测试。测试结果表明,微波源回旋管输出微波功率 达到1MW/3s,在真空度为 10^‒2Pa 的过模波纹圆波导传输线中能低耗稳定传输,发射天线极向全量程角度转动响 应时间在 50ms 以内。      

The Efficient Synthesis of Two Prostaglandin Intermediates

This paper presents new synthetic routes for methyl cis-7-iodo-5-heptenoate (7) and 3-hydroxycyclopent-2-enone (15a), useful intermediates in the synthesis of prostanoids.     

C-H-pi interactions in 1-n-butyl-3-methylimidazolium tetraphenylborate molten salt: solid and solution structures

The crystal structure of 1-n-butyl-3-methylimidazolium tetraphenylborate molten salt (1) shows C-H-pi interactions between the hydrogens of the imidazolium cation and the phenyl rings of the tetraphenylborate anion. The imidazolium ring is surrounded by three tetraphenylborate anions that are connected with the same cation by C-H-pi (phenyl rings) interactions. The nearest inter-ion interaction is found between the N-CH-N proton of the cation and the B-phenyl centroid (2.349 A) with a nearly T-shaped geometry. The inter-ionic solution structure of 1 has been investigated by the detection of inter-ionic contacts in 1H NOESY NMR spectra between the protons of the cation and the anion. The 1H-NMR spectra of molten salt 1 is almost independent of its concentration in [D6]DMSO solution, the imidazolium proton chemical shifts are in the expected region and there are no observable NOE effects between the protons of the cation with those of the anion, indicating that 1 behaves in [D6]DMSO as a solvent-separated ion pair. In CDCl3 the 1H-NMR spectra of 1 are concentration dependent and all the imidazolium protons are shielded as compared with those observed in [D6]DMSO. Moreover, the 1H NOESY NMR spectra show all the peaks affected by the interaction between the protons of the imidazolium cation and those of the anion, indicating that in CDCl3 1 possesses a contact ion pair structure. The NCHN proton of the cation exhibits the greatest shielding (up to -4.5 ppm). an indication of the existence of C-H-pi interactions, even in solution. The calculated distance of this proton to the phenyl centroid is 2.3 A for a C-H -pi angle of 180 degrees. The apparent volumes for the cation and anion, calculated from the measured 13C-NMR relaxation times, increase from 38 and 140 A3 in [D6]DMSO to 360 and 600 A3 in CDCl3, respectively; this indicates the formation of floating aggregates of the type (1)(n) in CDCl3 via weak hydrogen bonds, with increasing concentration.     

Effects of Adsorbed Polyaniline on Redox Processes on As(2)O(3) Surfaces

Polyaniline deposited on As(2)O(3) surface resulted in a new material, which was characterized by infrared spectoscopy, thermogravimetry, differential scanning calorimetry, scanning electron microscopy, X-ray diffraction, and cyclic voltammetry. The mass percentage of polymer deposited on oxide surface is approximately 13%. The scanning electron microscopy images as well as the X-ray diffraction patterns provided conclusive evidence that the oxide surface is coated by the polymer. The cyclic voltammograms of the polyaniline adsorbed on As(2)O(3) surface showed that the adsorbate exerts remarkable effects on redox processes on this oxide. The pure oxide exhibited two oxidation/reduction peaks at 0.25/-0.06 and 0.47/-0.25 V attributed tentatively to the processes As(2)O(3)(s)+6H(+)+6e(-)=2As(s)+3H(2)O and As(s)+3H(+)+3e(-)=AsH(3)(g), respectively. The polyaniline-coated sample exhibited a better-defined voltammogram in which the first oxidation peak of the oxide had its intensity increased about four times. Copyright 2000 Academic Press.