Ageing of wet-synthesized oxide powders

Wet chemical synthesis of precursor oxide ceramics is a method to obtain small particulate powders. Such powders are far more prone to ageing in air than more traditional precursors. Thermogravimetric analysis is used to highlight the species responsible for the ageing of ceramic precursors. Indeed water and carbon dioxide are observed to evolve from aged powders. Ceramics obtained from aged precursors can reach a very low final density with respect to the theoretical value. A large degree of the original sintering properties can be recovered after washing the aged powders with ethanol in a basic medium.     

ρ混合、φ混合、ψ混合线性模型M估计的强相合性

研究了 ρ混合、φ混合、ψ混合样本线性模型中回归参数M估计的强相合性 ,在条件不变的情况下 ,获得与独立情形一样的M估计是强相合的充分条件 ,推广了文 [1 ]定理 2 .     

ZnS and ZnSe Nanoparticles via Solid-State and Solution Thermolysis of Zinc Silylchalcogenolate Complexes

The thermolysis of the zinc trimethylsilylchalcogenolate complexes (N,N′-tmeda)Zn(ESiMe₃)₂ (E = S, 1; E = Se, 2) and (3,5-Me₂-C₅H₃N)₂Zn(ESiMe₃)₂ (E = S, 3; E = Se, 4) has been investigated. Solid-state thermal decomposition of complexes 1–4 above 250°C results in the formation of hexagonal ZnS and cubic ZnSe, respectively, via the liberation of TMEDA (1–2) or 3,5-lutidine (3–4) and E(SiMe₃)₂. Solid-state or solution thermolysis of these complexes up to 200°C produces nanocrystalline ZnS and ZnSe materials whose surface is protected by either coordinated TMEDA or 3,5-lutidine ligands. The progress of the step-wise solid-state decomposition of these complexes was monitored by thermogravimetric and single differential thermal analysis and volatile decomposition products in both solution and solid-state experiments were identified by GC/MS.Dedicated to Professor Brian F. G. Johnson on the occasion of his retirement.     

Duality in parameter space and approximation of measures for mixing repellers

For one-dimensional expanding mapsT with an invariant measure we consider, in a parameter space, the envelope _n of the real lines associated to any couple of points of the orbit, connected byn iterations ofT. If the map hass inverses and is piecewise linear, then the sets _n are just the union ofs ⁿ points and converge to the invariant Cantor set ofT. A correspondence between all the sets and their measures is established and allows one to associate the atomic measure on ₁ to the completly continuous measure on the Cantor set. If the map is nonlinear, hyperbolic, and hass inverses, the sets _n are homeomorphic to the Cantor set; they converge to the Cantor set ofT and their measures converge to the measure of the Cantor set whenn. The correspondence between the sets _n allows one to define converging approximation schemes for the map an its measure: one replaces each of thes ⁿ disjoint sets with a point in a convenient neighborhood and a probability equal to its measure and transforms it back to the original set ₁. All the approximations with linear Cantor systems previously proposed are recovered, the converging proprties being straightforward in the present scheme. Moreover, extensions to higher dimensionality and to nondisconnected repellers arte possible and are briefly examined.     

A Study of Amorphous Precursors for PbZrO3-PbTiO3 Based Ceramic Materials

Amorphous precursors for PbZrO₃ and PbTiO₃ ceramics were prepared from lead acetate and the transition metaln-propoxide inn-propanol orn-butoxide inn-butanol and hydrolysed with an excess of water. According to GLC and TGA/EGA analyses, the type of alkoxide group influences distinctly the structure of heterometallic precursors, i.e., oxo or acetate bridging, and the amounts of hydroxyl and organic groups bound to the metal network. The local environments of metal atoms in the amorphous precursors were also studied by EXAFS. The analysis reveals that in Pb−Zr precursors alkoxide groups modify the coordination spheres of the zirconium atoms. Conversely, local environments of both lead and titanium atoms within the analysed range of 3.4 A depend weakly on the type of alkoxide used.     

Synthesis of Phosphaformamidines and Phosphaformamidinates

A large‐scale synthetic route to a variety of phosphaformamidines and phosphaformamidinates, a type of derivative that was not accessible by the methods previously known for preparing phosphaamidines and phosphaamidinates, is reported. Thermally stable ethyl N‐arylformimidates 1 (ArN?CH(OEt), Ar=2,4,6‐(Me)₃Ph or 2,6‐(iPr)₂Ph) readily reacted with lithium dialkyl‐ and diarylphosphanides to afford the corresponding N‐aryl phosphaformamidines in 80 and 60 % yield, respectively, whereas with lithium (aryl)(silyl)phosphanide, the N‐aryl‐N‐silylphosphaformamidine (60 % yield) was obtained. Addition of primary lithium arylphosphanides to 1 followed by addition of a stoichiometric amount of nBuLi gave rise to the respective phosphaformamidinates (70–88 % yield). Methanolysis of the products afforded the N‐aryl‐N‐hydrogenophosphaformamidines (90–95 % yield). The solid‐state structure of one of the phosphaformamidinates is also presented.     

SXI route to mesostructured materials from Fau and Beta zeolite precursors: A comparative study of their assembly behaviors in extremely acidic media

Mesoporous molecular sieves were synthesized from Beta and Fau zeolite precursors through S⁺X⁻I⁺ route under extremely acidic conditions in parallel (designated as M_Beta and M_Fau, respectively). The textural properties of M_Fau were different from its M_Beta counterpart but resembled normal MCM-41 silica from TEOS. Al content in M_Beta was almost equivalent to that in the initial Beta zeolite precursors, whereas only trace Al species was present in M_Fau from elemental analysis results. The hydrothermal stability of M_Beta after post-synthesis ammonia treatment was considerably improved compared with normal MCM-41 aluminosilicates, whereas the M_Fau after the same procedure was as unstable as normal MCM-41 silica. Thus, the assembly behaviors of Beta and Fau zeolite precursors were comparatively studied based on these results. The microstructure of Fau zeolite precursors were degraded by the extremely acidic condition, and Al species was dissolved into the synthesis mixture. However, Beta zeolite precursors survived the chemical attack of extremely acidic media and were incorporated into mesostructured framework as primary building units.     

A Biokinetic Model to Describe Consequences of Inhibition/Stimulation in DNA-Proofreading and -Repair,Part 2. Calibration of the Model

Summary.  A biokinetic model has been developed to describe the mathematical consequences of inhibition, respectively stimulation of proofreading. According to data reported in the literature, a first approximative calibration of the model has been carried out in an attempt to make it both: practically applicable and comparable with experimental data and clinical facts. The model is open for further improvements and adjustable according to results of further researches via the parameters chosen. In a first test of the model it is shown that it does well reflect the results described in the literature upon proof-reading-inhibition and its consequences, i.e., the reduction of replication-fidelity (→ exponential increase of malignant cells with time). As a further result it is shown that the model also does well describe in its kinetic approach opposite effects as, e.g., a reduction of wrong genetic information by classical cancer-therapies like chemotherapy and surgergy. The system is orientated towards known biochemical relations and chemical similarities together with a discussion of the potential chance which offer special combinations of chemically identifyable substances (like nucleotides’ precursors or effector-molecules contained in low-molecular-human-placenta-extracts as an alternative to umbilical cords’-blood/cells) as stimulators of the enzymatic proof-reading- and -repair-machinery. E-mail: Haschke.H@isovolta.com Received January 20, 2002; accepted (revised) June 26, 2002     

Effects of viscosity on droplet formation and mixing in microfluidic channels

This paper characterizes the conditions required to form nanoliter-sized droplets (plugs) of viscous aqueous reagents in flows of immiscible carrier fluid within microfluidic channels. For both non-viscous (viscosity of 2.0 mPa s) and viscous (viscosity of 18 mPa s) aqueous solutions, plugs formed reliably in a flow of water-immiscible carrier fluid for Capillary number less than 0.01, although plugs were able to form at higher Capillary numbers at lower ratios of the aqueous phase flow rate to the flow rate of the carrier fluid (in all the experiments performed, the Reynolds number was less than 1). The paper also shows that combining viscous and non-viscous reagents can enhance mixing in droplets moving through straight microchannels by providing a nearly ideal initial distribution of reagents within each droplet. The study should facilitate the use of this droplet-based microfluidic platform for investigation of protein crystallization, kinetics, and assays.     

CHAOS FOR MIXING TRANSFORMATIONS

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