Formation of Polymeric Lewis Acid–Lewis Base Complexes with Well-defined Organoboron Polymers

The binding of Lewis bases to organoboron polymeric Lewis acids has been studied and the parameters that determine the complexation equilibrium have been investigated, which include (i) the strength of the individual Lewis acids and Lewis bases, (ii) concentration, and (iii) temperature. While the strongly Lewis acidic borane polymers poly(4-bis(pentafluorophenyl)borylstyrene) (PS-BPf) and poly(4-(di-2-thienylboryl)styrene) (PS-BTh) form isolable complexes with strong Lewis bases such as 4-t-butylpyridine (^tPy), a temperature dependent equilibrium is established with weaker bases such as THF. Similarly, the weakly Lewis acidic boronate polymer poly(4-diethoxyborylstyrene) (PS-BOEt) undergoes a temperature dependent equilibrium with the strong Lewis base 4-dimethylaminopyridine (DMAP), while poly(4-pinacolatoborylstyrene) (PS-BPin) does not significantly bind to pyridine bases. Decomplexation of PS-BTh· ^t Py is achieved by treatment with the stronger Lewis acid, B(C₆F₅)₃, thereby confirming the reversible nature of the polymeric Lewis acid–base adducts. This paper is dedicated to Professor Ian Manners in gratitude of his guidance throughout the years and recognition of his scientific accomplishments     

Sterol metabolism in the opportunistic pathogen <Emphasis Type="Italic">Pneumocystis</Emphasis>: Advances and new insights

Pneumocystis can transiently colonize healthy individuals without causing adverse symptoms, and most people test positive for exposure to this organism early in life. However, it can cause Pneumocystis pneumonia (PcP) in people with impaired immune systems and is a major cause of death in HIV/AIDS. Although it has close affinities to the Ascomycetes, Pneumocystis has features unlike those of any single group of fungi. For example, Pneumocystis does not synthesize ergosterol, which is consistent with the inefficacy of amphotericin B and some triazoles in clearing PcP. Pneumocystis sterols include distinct Δ⁷ 24-alkylsterols. Metabolic radiolabeling experiments demonstrated that P. carinii synthesizes sterols de novo. Cholesterol is the most abundant sterol in Pneumocystis; most, if not all, is scavenged from the mammalian host lung by the pathogen. The P. carinii erg7, erg6, and erg11 genes have been cloned, sequenced, and expressed in heterologous systems. The recombinant P. carinii S-adenosyl-l-methionine:C-24 sterol methyl transferase (SAM:SMT) has a preference for lanosterol over zymosterol as substrate, and the enzyme can catalyze the transfer of either one or two methyl groups to the C-24 position of the sterol side chain. Two different sterol compositions were detected among human-derived P. jirovecii; one was dominated by C₂₈ and C₂₉ sterols, and the other had high proportions of higher molecular mass components, notably the C₃₂ sterol pneumocysterol. The latter phenotype apparently represents organisms blocked at 14α-demethylation of the sterol nucleus. These studies suggest that SAM:SMT is an attractive drug target for developing new chemotherapy for PcP.     

Adsorption on activated carbon in countercurrent flow: An experimental study

The work describes adsorption experiments from aqueous solutions on activated carbon using a counter-current adsorber. Phenol and paranitrophenol were used for single component adsorption and molasses colour for multicomponent adsorption experiments. Isotherms were determined using simple equilibrium experiments. Three different techniques were used for determination of the kinetics. These were finite bath, infinite bath and fixed bed experiments. A mathematical model for countercurrent adsorption was tested. The model includes the effect of film diffusion and pore diffusion as well as surface diffusion, and can handle systems with a nonlinear isotherms. Kinetic data in the form of an average diffusivity in the carbon determined from the finite bath experiments and isotherm data did not predict the operation of the countercurrent column well. Data from the fixed bed experiments predicted countercurrent column operation much better. This is deemed to be due to inhomogeneities in the carbon used, resulting in a fairly quick initial uptake of the main part of the solute and a slower uptake of a minor amount.     

Cycling hardening and serration yielding of Fe-Ni-Cr alloy at high temperature under out-phase TMF

Behaviour of hardening and serration yield of a Fe-Ni-Cr alloy under isothermal cycling (ISC) and out-phase TMF was studied on the basis of varied hysteresis loops. Cycling hardening and serrated yielding for ISC depend on the temperature and the total strain range, stronger hardening with serrated yielding at higher strain range under ISC at 600 °C, but no hardening and serrated yielding occurred under ISC at 800 °C. Stronger hardening with stress serration occurred at the thermal path going to the lowest temperature, no stress serration occurred at the highest temperature under the out-phase. The hardening also depends on the total strain range, higher total strain range with lower cycling temperature resulted in a stronger hardening and remarkable serration yielding behavior. Weaker hardening without serrated yielding occurred at near 800 °C may due to an obvious cycling stress drop under out-phase TMF. Change in the shape of the hysteresis loops also expresses the degree of the damage of the tested alloy under out-phase and ISC.     

Fabrication and characterization of nano silver powder prepared by spray pyrolysis

Silver powder was fabricated by spray pyrolysis, using 2%–20% AgNO₃ solution, 336–500 mL/h flux of AgNO₃ solution, 0.28–0.32 MPa flux of carrier gas and in the 620–820 °C temperature range. The effects of furnace set temperature, concentration of AgNO₃ aqueous solution, flux of AgNO₃ aqueous solution as well as carrier gas on the morphology and particle size distribution of silver powder, were investigated. The experimental results showed that with the high concentration of AgNO₃ aqueous solution, the average grain size of silver decreased with the increasing of furnace set temperature. But the gain size distribution was not homogenous, the discontinuous grain growth occurred. With the low concentration of AgNO₃ aqueous solution, the higher furnace set temperature made the nano sliver grains sintered together to grow. Nano silver powder about 100 nm was fabricated by spray pyrolysis, using 2wt% AgNO₃ solutions, 336 mL/h flux of AgNO₃ aqueous solution, 0.32 MPa flux of carrier gas at 720 °C furnace set temperature.     

Research on the friction and wear mechanism of Poly(vinyl alcohol)/hydroxylapatite composite hydrogel

Poly(vinyl alcohol)/Hydroxylapatite (PVA/HA) composite hydrogel was prepared with poly(vinyl alcohol) and hydroxylapatite as raw materials, using the method of repeated freezing and thawing. The morphologies of PVA/HA composite hydrogel were observed by means of high-accuracy 3D profiler and scanning electron microscope (SEM). The compressive elastic modulus and the stress relaxation characteristics of PVA/HA composite hydrogel were measured using the flat-head cylinder indenter. The friction and wear tests between PVA/HA composite hydrogel and bovine knee articular cartilage were performed on the micro-tribometer. The worn morphologies of PVA/HA composite hydrogel were observed with environmental scanning electron microscope (ESEM). The results showed that PVA/HA composite hydrogel has the cross-link network microstructure which is similar to that of the natural bovine knee articular cartilages. With the increase of freezing-thawing cycles and the HA content, the degree of cross-link and the crystallization of PVA/HA composite hydrogel both increase, the elastic modulus increases evidently, the rate of stress relaxation is improved and the value of balance stress decreases. The friction coefficient decreases with the increase of the freezing-thawing cycles and the HA content. The more the freezing-thawing cycles are, the earlier the friction coefficient reaches the stable balance value. The friction deformation depth between PVA/HA composite hydrogel and bovine knee articular cartilage is inversely proportional to freezing-thawing cycles and the HA content. The main wear mechanisms of PVA/HA composite hydrogel are plastic flowing and adhesive flaking. The wear severity degree decreases with the increase of freezing-thawing cycles and the HA content. Supported by Key Program of the National Natural Science Foundation of China (Grant No. 50535050), Program for New Century Excellent Talents in University (Grant No. NCET-06-0479) and Natural Science Foundation of Jiangsu Province (Grant No. BK2005403)     

A macro-meso constitutive law for concrete having imperfect interface and nonlinear matrix

The overall behavior of concrete depends on its meso structures such as aggregate shape, interface status, and mortar matrix property. The two key meso structure characters of concrete, bond status of interface and nonlinear property of matrix, are considered in focus. The variational structure principle is adopted to establish the macro-meso constitutive law of concrete. Specially, a linear reference composite material is selected to make its effective behavior approach the nonlinear overall behavior of concrete. And the overall property of linear reference composite can be estimated by classical estimation method such as self-consistent estimates method and Mori-Tanaka method. This variational structure method involves an optimum problem ultimately. Finally, the macro-meso constitutive law of concrete is established by optimizing the shear modulus of matrix of the linear reference composite. By analyzing the constitutive relation of concrete established, we find that the brittleness of concrete stems from the imperfect interface and the shear dilation property of concrete comes from the micro holes contained in concrete. Supported by the National Natural Science Foundation of China (Grant Nos. 50679022, 90510017, 50539090) and National Basic Research Program of China (Grant No. 2007CB714104)     

Discrimination for ablative control mechanism in solid-propellant rocket nozzle

The ablation in solid-propellant rocket nozzle is a coupling process resulted by chemistry, heat and mass transfer. Based on the heat and mass transfer theory, the aero-thermo-dynamic, and thermo-chemical kinetics, the thermal-chemical ablation model is established. Simulations are completed on the heat flow field and chemical ablation in the nozzle with different concentrations, frequency factors and activation energy of H2. The calculation results show that the concentration and the activation energy of H...     

Reaction mechanism and microstructure evolution of reaction sintered <Emphasis Type="Italic">h</Emphasis>-BN

Hexagonal boron nitride ceramic (h-BN) based on the nitridation of B powders was obtained by reaction sintering method. The effects of sintering temperature on the mechanical properties and microstructure of the resultant products were investigated and the reaction mechanism was discussed. Results showed that the reaction between B and N₂ occurred vigorously at temperatures ranging from 1 000 °C to 1 300 °C, which resulted in the generation of t-BN. When the temperature exceeded 1 450 °C, transformation from t-BN to h-BN began to occur. As the sintering temperature increased, the spherical particles of t-BN gradually transformed into fine sheet particles of h-BN. These particles subsequently displayed a compact arrangement to achieve a more uniform microstructure, thereby increasing the strength.     

Optimization of uncertain acoustic metamaterial with Helmholtz resonators based on interval model

Uncertainties existing in the acoustic metamaterial may strongly affect its unusual properties. Aiming at this actuality, the interval model is introduced to treat with uncertainties existing in the acoustic metamaterial with Helmholtz resonators. Frequency intervals in which the sound intensity transmission coefficients are certainly less than the required value and the effective bulk moduli are certainly negative are defined as conservative approximations. Frequency intervals in which the sound intensity transmission coefficients may be less than the required value and the effective bulk moduli may be negative are defined as unsafe approximations. The proportion of the conservative approximation and the unsafe approximation is defined as an approximate precision. Based on the quantification of uncertainties of the sound intensity transmission coefficients and the negative effective bulk moduli, an optimization model for the interval acoustic metamaterial with Helmholtz resonators is constructed. Numerical results showed that even suffering from effects of interval parameters, unusual properties of the optimized acoustic metamaterial (such as the bandgap of the sound transmission and the negative effective bulk modulus) could be improved.