Novel iron carbonyl complexes from thiophene-2-carboxaldehyde thiosemicarbazone

The reaction of thiophene-2-carboxaldehyde thiosemicarbazone (2-C₄H₃SCHNNHC(S)NH₂) (1) with diiron nonacarbonyl under mild conditions in anhydrous benzene yields three iron carbonyl organometallic clusters: (i) Fe₂S₂ square-base pyramidal cluster 2 ([Fe(CO)₃]₃(μ₃-S)₂), (ii) Fe₂S₂ square-base pyramidal metal carbene cluster 3 ([Fe(CO)₃]₂Fe(CO)₂(μ₃-S)₂(C(NH₂)NHNCH (2-C₄H₃S)), and (iii) double butterfly cluster 4 ([Fe(CO)₃]₃Fe(CO)₂(μ₄-S)(C,N; C(NH₂)NHNCH(2-C₄H₃S) (μ₂-S, N; SC(NH₂)NNCH(2-C₄H₃S)), and an octahedral complex 5 (Fe(CO)₂(S, N; SC(NH₂)NNCH (2-C₄H₃S))₂. These products were fully characterized spectrally. The molecular structures of 1, 3, 4, and 5 have been determined by single-crystal X-ray diffraction.     

A unique reaction pathway of fluorine-substituted ethyl groups on Cu(111): successive alpha,alpha-fluoride elimination

Fluorine-substituted ethyl groups on Cu(111) were generated by thermal scission of the C-I bond in the adsorbed C2F5I. Temperature-programmed reaction spectrometry observed a novel pathway resulting in the evolution of C4F6 above 400 K. Among the various isomers, this product was identified as hexafluro-2-butyne. Although abstraction of two fluorine atoms from the starting Cu-CF2CF3 was required, Cu-CCF3 (trifluoroethylidyne) was favored over Cu-CF=CF2 (trifluorovinyl) as the intermediate because this ethyl-ethylidyne-butyne pathway was suppressed on a Cu(100) surface devoid of the key threefold hollow binding sites for ethylidyne. Once formed, perfluoroethylidyne readily coupled to afford a tightly surface-bound hexafluoro-2-butyne up to 400 K. Therefore, the C-F bonds adjacent to the metal were found to be more susceptible to the bond activation, leading the chemisorbed perfluoroethyl to eliminate two F atoms successively from the alpha-carbon. This preference for alpha-elimination rather than beta-elimination (the most favorable route in hydrocarbons) may be quite general for metal surface-mediated reactions involving fluorinated alkyl groups.     

Alternating layer and island growth of Pb on Si by spontaneous quantum phase separation

Real-time in situ x-ray studies of continuous Pb deposition on Si(111)-(7x7) at 180 K reveal an unusual growth behavior. A wetting layer forms first to cover the entire surface. Then islands of a fairly uniform height of about five monolayers form on top of the wetting layer and grow to fill the surface. The growth then switches to a layer-by-layer mode upon further deposition. This behavior of alternating layer and island growth can be attributed to spontaneous quantum phase separation based on a first-principles calculation of the system energy.     

Propagation characteristics of a segmented cladding fiber

We propose a novel optical fiber design that consists of a uniform core and a segmented cladding formed by alternate regions of high and low refractive indices in the azimuthal direction. The structure is analyzed by use of the radial effective-index method, and the propagation characteristics of the structure are studied. The fiber has a highly dispersive cladding and shows characteristics similar to those of photonic-crystal fibers and holey fibers. The novel fiber offers the possibility of single-mode operation over a wide range of wavelengths with a large core diameter.     

Preparation of Zirconia Nanocrystals from Concentrated Zirconium Aqueous Solutions

A high concentration (0.8 M) zirconium solution turned into a stable aqueous colloid of about 60 nm in size upon low temperature (96^°C) incubation. Changing the acid concentration did not affect the colloidal growth rate nor the final colloid size much. However, the induction time before the rapid growth of colloidal particle could be altered. By limiting the incubation to just before the rapid growth of colloidal zirconia, and the addition of organic acids as surface modifiers, non-agglomerated primary crystallites (10 nm) of m-ZrO₂ could be recovered. These modified primary crystallites could then be repeatedly flocculated and redispersed in water by adjusting the pH.     

Multiple nano-TiO2 layers to prevent dye/nano-TiO2 from photodegradation under a UV-exposure environment

A device of multiple nano-TiO₂ layers was proposed and fabricated to prevent a dye/nano-TiO₂ region from serious photo-degradation. In this device, the top of the dye/TiO₂ region was designed to be coated using sol-gel nano-TiO₂ thin films to shield UV irradiation from the photo-degradation effect. The sol-gel TiO₂ was prepared in a low temperature (75 °C) and verified as nano-sized particles and an anatase crystalline structure. Different devices of the multi-layer samples fabricated using different compositions of nano-TiO₂ were produced and exposed for UV irradiation tests. Results show that the presence of the sol-gel TiO₂ films coated on top of the dye/TiO₂ region can significantly alleviate the dye photo-degradation under UV irradiation. This multi-layer device can effectively improve the photo-stability of the dye/TiO₂ region in a UV-exposure environment.     

Rank procedures for testing subhypotheses in linear regression

Summary In the linear regression modelX _i=α+βc_i+Z_i, we consider the problem of testing the subhypothesis that some (but not all) components of β are equal to 0. A class of asymptotically distribution-free tests based on a quadratic form in aligned rank statistic is studied and the asymptotic relative efficiencies of the proposed tests with respect to the general likelihood ratio test and the test based on least-squares estimates of regression parameters are derived. Asymptotic optimality (à la Wald) is also discussed. Work done under the National Science Foundation Grant MCS 8301409 and NATO Grant 1465.     

Constituents of Antrodia Cinnamomea

We describe identification of seven components from Antrodia cinnamomea. Their structures were determined on the basis of spectral analysis and comparison with authentic samples. These compounds include two steroids (1, 2) (β-sitosterol and eburicol), two new steroids (3, 4) [methyl-4α-methylergost-8,24(28)-dien-3,7,11-trion-26-oate and methyl-4α-methylergost-8,24(28)-dien-3,11-dion-26-oate], two lignans (5, 6) [(+)-sesamin and 4-hydroxysesamin], and one long chain methyl ester (7) (methyl oleate). Among them, compounds 3 and 4 are first isolated from nature.     

Adsorptive stripping voltammetry of some trace elements in biological samples,II: Nickel,arsenic, aluminium and selenium

A study of the adsorptive stripping voltammetry of nickel, aluminium, selenium and arsenic is reported in which 2,5-dimercapto-1,3,4-thiadiazole (DMTD) has been used as a chelating agent. By a suitable choice of deposition potential, deposition time, reagent reaction time and other operating conditions, the determination of the four elements could be achieved.By the use of benzyltrimethyl ammonium methoxide as a digesting solvent, it was possible to apply the procedure to the direct determination of the four elements in biological samples.