Eine neue Hochtemperaturform von TiO: H?TiO

A New High Temperature Form of TiO: H? TiO Single crystals of a high temperature form of TiO (H? TiO) were prepared above 3 000°C by CO₂-LASER technique. They crystallize with a hitherto unobserved crystal structure of oxides with titanium in the oxidation state two, isotypic to tungsten carbide with Ti²⁺ in a trigonal prismatic surrounding by oxygen. Space group D–P6 m2, a = 3.0310, c = 3.2377 Å, Z = 1.     

Stereoselective titanium-mediated aldol reactions of (S)-2-tert-butyldimethylsilyloxy-3-pentanone

Titanium-mediated aldol reactions based on (S)-2-tert-butyldimethylsilyloxy-3-pentanone, a lactate-derived chiral ketone, provide the corresponding 2,4-syn-4,5-syn adducts in high yields and diastereomeric ratios with a wide array of achiral and chiral aldehydes. Furthermore, spectroscopic studies of intermediates involved in the process have permitted to propose a mechanism that accounts for the experimental results.     

The Adsorption and Photocatalytic Decomposition of Citric Acid on Pt/TiO_2

The adsorption and photocatalutic decomposition of citric acid on both Pt/TiO2 powder and n-TiO2 single crystal electrode were studied in aqueous solutions of various pH. It was found that citrate ions were chemisorbed on TiO2, which could increase the interfacial capacity and the filling factor of photocurrent-potential curves. The quantity of adsorption, slope of mott-Shottky plot and the rate of photocatalytic decomposition of citric acid were found to depend strongly on pH of solution. The phot ocatalytic decomposition of citric acid was discussed in light of its adsorption on TiO2.     

电热蒸发进样—等离子体原子发射光谱中钒和钛的蒸发机理研究

自1974年Nixon报道钽丝电热蒸发作为ICP-AES进样技术以来,这一技术已引起了人们的极大兴趣,受到越来越广泛的重视。电热蒸发(ETV)-ICP-AES是一种将蒸发和激发分步进行的联用技术。石墨是目前普遍使用的蒸发器材料。然而,在高温下某些元素和石墨材料可以发生碳化反应,形成热稳定的碳化物,使分析物蒸发不完全或根本不蒸发,从而影响分析结果的灵敏度和准确性。为了解决这一问题,我们曾提出了以聚四氟乙烯(PTFE)悬浮体为氟化剂,氟化辅助ETV-ICP-AES直接测定粉煤标样中钒和钛的新方法,其检出限     

All Solid‐State pH Electrode Based on Titanium Nitride Sensitive Film

Titanium nitride was used as pH‐sensitive material to fabricate all solid‐state pH electrode. The fabrication and the response performance of the pH electrode were described in the paper. The TiN film electrode showed a linear response in the pH range of 2–12 with a near‐Nenstian response (?55 mV/pH). The response time was within 1 min, and the electrode had good reproducibility, stability and low sensitivities for different species. Compared with the glass pH electrode, the electrode exhibited some advantages, for example, without activation, rapid response and high mechanical strength. In addition, the electrode performed excellently in a corrosion medium containing F^?(1 M). Electrochemical behaviors of TiN electrode in Britton‐Robinson buffers were studied with Electrochemical Impedance Spectroscopy (EIS).     

Novel Knöevenagel-type reaction via titanium enolate derived from Ti(O-i-Pr)4 and diketene

Knöevenagel-type reaction between diketene and aldehydes proceeded in the presence of Ti(O-i-Pr)₄. This reaction proceeded via titanium enolate derived from Ti(O-i-Pr)₄ and diketene. As for the stereoselectivity of the products, E-isomers were produced predominantly in the case of aromatic aldehydes.     

Electrochemical behaviour of some polyoxo clusters

We describe the redox behaviour in non-aqueous solvents of some cyclopentadienyl(oxo)titanium derivatives. The derivative [Ti₄{η⁵-C₅H₄(SiMe₃)}₄(μ-O)₆] shows an electrochemically and chemically reversible le reduction process, followed by a multi-electron, chemically complicated reduction at a fairly cathodic potential. On the basis of the overall electrochemical features and the comparison with the redox behaviour of the quasi-planar compound [[Ti{η⁵-C₅H₄(SiMe₃)}Cl(μ-O)]₄] we propose an EECCEE mechanism for the first derivative, where the second electron-transfer induces a cascade of chemical reactions giving rise to irreversible cluster breakdown. The electrochemically induced fragmentation can be viewed as a retrosynthetic pathway. The heterometallic derivative [{Ti(η⁵-C₅H₄Me)₂(μ₂-MoO₄)₂}₂] shows two consecutive reduction processes; the first is chemically reversible, and the second quasi-reversible. The molybdate bridges apparently increase the stability of the electrogenerated anions. However none of these poly-oxo clusters can be considered as good models of electron ‘sinks’.     

Online photocatalytic device for highly selective pre-column fluorescence derivatization of 5-hydroxyindoles with benzylamine

A fluorimetric liquid chromatographic method for the determination of 5-hydroxyindoles based on the benzylamine derivatization process mediated through an online photocatalytic oxidation has been developed. In this study, we used a photocatalytic column comprising tefzel tubing packed with TiO₂-coated glass beads, as a pre-column derivatization reactor. The fluorescence derivatization of 5-hydroxyindoles using benzylamine proceeded during their passage through the reaction column under near-UV irradiation. The 5-hydroxyindole derivatives were separated continuously on a reversed-phase liquid chromatography within 50 min, using 100 mM acetate buffer (pH 4.6)-acetonitrile (72:28, v/v; isocratic elution) containing 3 mM sodium octanesulfonate; the samples were detected fluorimetrically at 465 nm upon excitation at 350 nm. The detection limits (signal-to-noise ratio = 3) of the 5-hydroxyindoles were in the range from 160 to 360 fmol per 5 μL injection. We have applied this method, which requires minimal sample pre-treatment, to the determination of 5-hydroxyindole-3-acetic acid in human urine.     

Synthesis,characterization, and structural investigation of New η5-Cyclopentadienylbis-8-hydroxyquinolinatometal(IV) Complexes

By the interaction of M(η⁵-C₅H₄R)₂Cl₂ (M = Zr, Hf; R = H, Me, SiMe₃) and 8-hydroxyquinoline (oxH) or 5-chloro-8-hydroxyquinoline (ox′H) in dichloromethane solution at 20°C, the compounds M(η⁵-C₅H₄R)Clox₂ and M(η⁵-C₅H₄R)Clox₂′ were prepared respectively. A similar reaction of Ti(η⁵-C₅H₅)Cl₃ with ox′H in acetonitrile solution gave Ti(η⁵-C₅H₅)Clox₂′. All complexes were characterized by elemental microanalysis and by IR and ¹H NMR spectroscopy. X-ray analysis of M(η⁵-C₅H₅R)Clox₂′ (M = Ti, Hf) shows that these molecules may be described in terms of stereochemistry of eight-coordination approximating dodecahedral geometry more closely than octahedral geometry. With respect to octahedral coordination, the nitrogen atoms lie in a cis-configuration and the oxygen atoms in a trans-configuration. Dichloromethane molecules co-crystallize with the hafnium complex and occupy a position on the 2-fold axis. The structural results are compared with those in related compounds.     

Titanium as a chemical modifier for the determination of cobalt in marine sediments

The determination of cobalt in marine sediments by electrothermal atomic absorption spectrometry was studied using no modifier and magnesium and titanium as modifiers. Titanium is one of the major sediment constituents, which widely affects the cobalt determination and it was studied as a chemical modifier since it was the only concomitant that increased the cobalt signal in the concentration range usually found in sediments. The performance of Mg and Ti as chemical modifiers was compared relative to maximum pyrolysis and atomization temperatures, linear calibration range, sensitivity and matrix effects. The pyrolysis curves showed that the analyte could be stabilized up to 1400 °C when either Ti or Mg(NO₃)₂ was present, while only 1000 °C could be used in the absence of a modifier. The optimum atomization temperature was 2500 °C in all cases. Analytical curves were compared using no modifier, 5 μg Ti and 100 μg Mg(NO₃)₂ as modifiers, and the linear range found was up to approximately 4 ng Co whether a modifier was used or not. With Ti as a chemical modifier, analytical curves for cobalt in aqueous solution and in a synthetic matrix resulted in the same sensitivity (m₀=55 pg), whereas the use of Mg led to characteristic mass values of 59 and 72 pg in aqueous solution and in a synthetic matrix, respectively, showing some matrix effect. The detection limits (3σ, n=10) were 0.4 μg g⁻¹ using no modifier and 0.3 μg g⁻¹ with Ti as a modifier in the original matrix. A reference estuarine sediment NIST 1646 with a non-certified content of 10.5 μg g⁻¹ Co was analyzed and the found value of 10.9±2.4 μg g⁻¹, (n=3), using Ti as chemical modifier and calibration against aqueous standards, was in good agreement with the recommended value.