Characterization of poly(diethoxyphosphazene) by size exclusion chromatography and viscometry

Two samples of poly(diethoxyphosphazene) (PDEP) having very different molecular weights have been studied by viscometry and size exclusion chromatography in THF solution. The results obtained, together with light scattering data of these samples, allow the calculation of the Mark-Houwink constants a=0.65 and K=2.5 10^-4 in THF at 25°C. The method of calculation employed takes into account the great polydispersity of the samples. The characteristic ratio of the unperturbed dimensions was also calculated giving C_n = r²_o/n² 18, a value slightly higher than those previously reported for poly(dihexoxyphosphazene), C_n13 and poly (dichlorophosphazene), C_n13.5.     

Hydrodynamic characteristics of a FCC regenerator

The hydrodynamic and gas mixing characteristics have been determined in a FCC regenerator (0.48 m I.D.x3.4 m high) with FCC particles. Solids holdup in the dense bed decreases with increasing gas velocity, but it increases in the freeboard region. The bubble/void fraction increases with an increase along the bed height at a given gas velocity and increases with increasing gas velocity at a constant bed height. Backmixed tracer gas at the wall region is higher than that at the center region of the bed. The gas backmixing coefficient decreases with increasing gas velocity.     

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     

Modelling the effects of human papillomavirus in cervical cells

Worldwide, cervical cancer is the second most common cancer in women, after breast cancer. The prevalence of this malignant disease is estimated at 1.4 million cases worldwide, causing about 290,000 deaths and 500,000 new cases per year, of which 80% correspond to women living in developing countries. In this work we propose a family of ordered models for basal cells of the cervix corresponding to different stages ranging from normal cells to the formation of precancerous lesions. We analyse the first member of the family analytically and for the second member we developed a non-standard numerical method in order to extract some biological information.     

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.     

A voltammetric study concerning the structural stability of Li-overstoichiometric Mg-doped LiCoO2 powders

The effect of Mg-doping and Li overstoichiometry on the structural stability of LiCoO₂ powders has been investigated with emphasis to voltammetric properties. Microparticle cyclic voltammetry (CV) conducted in caustic NaOH to best simulate a non-aqueous electrolyte shows a marked improvement of the structure stability of doped LiCoO₂. In contrast to the unsubstituted LiCoO₂ sample which shows voltammetric peaks associated to the well-known two-phase domain and monoclinic distortion reactions, in Li_1.08Mg_0.06CoO₂, LiMg_0.06CoO₂ and Li_1.08CoO₂ samples these peaks are strongly suppressed providing direct evidence for the existence of a stable solid solution with negligible phase transitions in the reversible intercalation region (3.8-4.2 V vs. Li) as well as in the overcharged region. The effect is higher with Mg-doping, irrespective of the Li overstoichiometry. However, the concomitant presence of Mg and Li excess in the structure is important for obtaining small particle sizes. Since Mg-doping induces a quasi metallic behavior in the samples, whereas the Li excess may provide an higher initial capacity, it is suggested that the Li_1.08Mg_0.06CoO₂ composition may be of interest as positive cathode for advanced Li-ion batteries.     

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)