In this paper, dielectric and calorimetric studies of the small-molecule glass former allyl acetoacetate monomers as well as its newly synthetized homopolymer and copolymers with different styrene composition were performed in both the liquid and glassy states. The molecular dynamics studies by the broadband dielectric spectroscopy and the stochastic temperature modulated differential scanning calorimetry enabled us to explore relaxation processes of examined materials in the wide frequency range. We found that the copolymers reveal two co-existing glass transitions characterized by the glass transition temperatures, which are very close to those of the corresponding homopolymers. These results suggest that the copolymers exhibited some sequences of acetoacetate units with a microphase-separated morphology in agreement with the value of reactivity ratio previously determined. We investigated effects of copolymerization compositions on the glass transition temperature, the isobaric fragility index, the dielectric and calorimetric intensity, and the dynamic heterogeneity on the glass transitions of the materials. 相似文献
This article examines the presence of the empirical tendency known as the Menzerath–Altmann Law (MAL) on protein secondary structures. MAL is related to optimization principles observed in natural languages and in genetic information on chromosomes or protein domains. The presence of MAL is examined on a non-redundant dataset of 4728 proteins by verifying significant, negative correlations and testing classical and newly proposed formulas by fitting the observed trend. We conclude that the lengths of secondary structures are specifically dependent on their number inside the protein sequence, while possibly reflecting the formula proposed in this paper. This behavior is observed on average but is individually avoidable and possibly driven by a latent cost function. The data suggest that MAL could provide a useful guiding principle in protein design. 相似文献
Diamond-Blackfan anaemia (DBA) is a red blood cell aplasia that in the majority of cases is associated with ribosomal protein (RP) aberrations. However, the mechanism by which this disorder leads to such a specific phenotype remains unclear. Even more elusive is the reason why non-specific agents such as glucocorticosteroids (GCs), also known as glucocorticoids, are an effective therapy for DBA. In this review, we (1) explore why GCs are successful in DBA treatment, (2) discuss the effect of GCs on erythropoiesis, and (3) summarise the GC impact on crucial pathways deregulated in DBA. Furthermore, we show that GCs do not regulate DBA erythropoiesis via a single mechanism but more likely via several interdependent pathways. 相似文献
Aiming to reduce the carbon dioxide emissions associated with cement production, alternative binders such as inorganic polymers currently receive substantial attention and slags from the non-ferrous metallurgy are promising precursors. However, studies that correlate their chemistry and crystallinity with the newly formed binder remain limited. In this work, the effect of three different solidification methods on glass formation and reactivity of FeOx–SiO2 slags, as well as on the molecular structure of the resultant Fe-rich inorganic polymers, was investigated. The inorganic polymers were synthesized by mixing the slags (approximate molar ratio FeO/SiO2 = 1.6) with an alkali silicate solution (molar ratios SiO2/Na2O = 1.6 and H2O/Na2O = 25). Results demonstrated that higher cooling rates promoted higher glass formation and faster reaction kinetics when the slags were activated. 57Fe Mössbauer spectroscopy indicated that all the slags consisted predominantly of Fe2+ ions with a minor amount of Fe3+ ions, regardless of the variability in glass content. The binder phase of all inorganic polymers consisted of iron in both Fe2+ and Fe3+ states, after 28 days of curing. After pulverizing the inorganic polymer pastes and exposing the powder to air for 28 additional days, the Fe2+ state in the binder transformed to Fe3+. The compressive strength evolution of the three slags showed that the 2-day strength was higher for the samples with a higher amorphous fraction, while after 28 days, this influence was less pronounced. 相似文献
We calculate the diffusion coefficients for ions moving in a prescribed electromagnetic field. Thefield is considered to be a superposition of an electrostatic stochastic field and a space-dependent and sheared magnetic field. We have considered as parameters involved in the calculation of the diffusion coefficients the shear ion Kubo number K_s~(ion), the electrostatic Kubo number K, the parallel shear ion Kubo number K_(zs)~(ion), and the parallel thermal ion Kubo number K_z~(ion).A geometrical parameter which is the measure of the product of the stochastic perpendicular correlation length and the gradient in the magnetic field strength(see definitions in the text) is found not to be important in our calculation. The results concerning the diffusion coefficients obtained in our model are in agreement with experimental data and with those corresponding to other models, and the neoclassical and anomalous values for the diffusion coefficients are obtained. 相似文献
The microstructure of inorganic polymers (IP) formed from fayalite slag was investigated as a function of the composition of different activating solutions. The starting slag was 80 wt% amorphous, and after activation using sodium silicate solutions with varying SiO2/Na2O molar ratios, the amorphous phase dissolved and a binder phase was formed. The morphology of this binder, including the population and size of remnant particles and pores, was dependent on the particular activating solution used, and became denser as the level of silicate rose. 57Fe Mössbauer spectroscopy revealed that the IP synthesis reaction is combined with the oxidation of Fe2+ from the fayalite slag to Fe3+ in the inorganic polymer binder. The reaction extent varied and could be quantified using the absorption areas of these ions. Data corroborate that the Fe2+ ions in the amorphous part of the fayalite slag and the Fe3+ ions in the new binder phase had an average oxygen‐coordination number of 5. 相似文献
Combustion of CO, ethyl acetate and ethanol was studied over CuOx/Al2O3, CuOx–CeO2/Al2O3, CuMn2O4/Al2O3 and Mn2O3/Al2O3 catalysts. It was found that modification of the alumina with ceria before subsequent copper oxide deposition increases the activity for combustion of CO substantially, but the effect of ceria was small on the combustion of ethyl acetate and ethanol. The activity increases with the CuOx loading until crystalline CuO particles are formed, which contribute little to the total active surface. The CuOx–CeO2/Al2O3 catalyst is more active than the CuMn2O4/Al2O3 catalyst for the oxidation of CO but the CuMn2O4/Al2O3 catalyst is more active for the combustion of ethyl acetate and ethanol.
Thermal ageing and water vapour in the feed caused a modest decrease in activity and did not affect the CuOx–CeO2/Al2O3 and CuMn2O4/Al2O3 catalysts differently. In addition, no difference in intermediates formed over the two catalysts was observed.
Characterisation with XRD, FT-Raman and TPR indicates that the copper oxide is present as a copper aluminate surface phase on alumina at low loading. At high loading, bulk CuO crystallites are present as well. Modification of the alumina with ceria before the copper oxide deposition gives well dispersed copper oxide species and bulk CuO crystallites associated to the ceria, in addition to the two copper oxide species on the bare alumina. The distribution of copper species depends on the ceria and copper oxide loading. The alumina supported copper manganese oxide and manganese oxide catalysts consist mainly of crystalline CuMn2O4 and Mn2O3, respectively, on Al2O3. 相似文献