连铸结晶器内部流场及熔渣卷入的数值模拟

针对连铸结晶器内部流场及熔渣卷入过程 ,提出了两方程k -ε湍流模型和充填法数值计算模型 ,并采用硅油 /水模拟体系代替熔渣 /钢液体系 ,进行了模拟试验和数值计算。对充气造成的浸入式水口水流脉动的影响进行分析。计算结果与试验结果符合良好 ,表明本文所采用的数值模拟方法是适用的     

Protein structure predictions by parallel simulated annealing molecular dynamics using genetic crossover

We propose a conformational search method to find a global minimum energy structure for protein systems. The simulated annealing is a powerful method for local conformational search. On the other hand, the genetic crossover can search the global conformational space. Our method incorporates these attractive features of the simulated annealing and genetic crossover. In the previous works, we have been using the Monte Carlo algorithm for simulated annealing. In the present work, we use the molecular dynamics algorithm instead. To examine the effectiveness of our method, we compared our results with those of the normal simulated annealing molecular dynamics simulations by using an α-helical miniprotein. We used genetic two-point crossover here. The conformations, which have lower energy than those obtained from the conventional simulated annealing, were obtained.     

Asymmetric synthesis of α,α-disubstituted α-amino alcohol derivatives

Herein we report the asymmetric synthesis of α,α-disubstituted α-amino alcohol derivatives 22, 25 and 26, key intermediates of a novel immunomodulator, using Seebach’s method. This synthetic method can be applied to the large scale synthesis of chiral sphingosine 1-phosphate-1 (S1P₁) receptor agonists, with significant improvements to the previously reported method with regard to the reaction temperature.     

1D and 2D assembly structures by imidazole···chloride hydrogen bonds of iron(II) complexes [Fe(II)(HL(n-Pr))3]Cl·Y (HL(n-Pr) = 2-methylimidazol-4-yl-methylideneamino-n-propyl; Y = AsF6, BF4) and their spin states

Two Fe(II) complexes fac-[Fe(II)(HL(n-Pr))(3)]Cl·Y (Y = AsF(6) (1) and BF(4) (2)) were synthesized, where HL(n-Pr) is 2-methylimidazole-4-yl-methylideneamino-n-propyl. Each complex-cation has the same octahedral N(6) geometry coordinated by three bidentate ligands and assumes facial-isomerism, fac-[Fe(II)(HL(n-Pr))(3)](2+) with Δ- and Λ-enantiomorphs. Three imidazole groups per Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) are hydrogen-bonded to three Cl(-) ions or, from the viewpoint of the Cl(-) ion, one Cl(-) ion is hydrogen-bonded to three neighbouring fac-[Fe(II)(HL(n-Pr))(3)](2+) cations. The 3?:?3 NH···Cl(-) hydrogen bonds between Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) and Cl(-) generate two kinds of assembly structures. The directions of the 3?:?3 NH···Cl(-) hydrogen bonds and hence the resulting assembly structures are determined by the size of the anion Y, though Y is not involved into the network structure and just accommodated in the cavity. Compound 1 has a 1D ladder structure giving a larger cavity, in which the Δ- and Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) enantiomorphs are bridged by two NH···Cl(-) hydrogen bonds. Compound 2 has a 2D network structure with a net unit of a cyclic trimer of {fac-[Fe(II)(HL(n-Pr))(3)](2+)···Cl(-)}(3) giving a smaller cavity, in which Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) species with the same chirality are linked by NH···Cl(-) hydrogen bonds to give a homochiral 2D network structure. Magnetic susceptibility and M?ssbauer spectral measurements demonstrated that compound 1 showed an abrupt one-step spin crossover with 4.0 K thermal hysteresis of T(c↓) = 125.5 K and T(c↑) = 129.5 K and compound 2 showed no spin transition and stayed in the high-spin state over the 5-300 K temperature range.     

Liquid phase formation of alkyl- and perfluoro-phosphonic acid derived monolayers on magnesium alloy AZ31 and their chemical properties

Alkyl- and perfluoro-phosphonic acid derived SAMs were successfully formed on Mg alloy by liquid phase method for the first time. The chemical and anticorrosive properties of the prepared SAMs on magnesium alloys were characterized using contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and electrochemical measurements. Water contact angle measurements revealed that the maximum advancing/receding water contact angles of n-octyl (OP: CH(3)(CH(2))(7)PO(OH)(2)), n-dodecyl (DP: CH(3)(CH(2))(11)PO(OH)(2)), n-octadecyl (ODP: CH(3)(CH(2))(17)PO(OH)(2)) phosphonic acid, and 2-(perfluorohexyl)ethyl (PFEP: CF(3)(CF(2))(5)CH(2)CH(2)PO(OH)(2)) phosphonic acid were 105.1/64.7°, 108.3/69.6°, 111.9/75.2°, and 115.2/67.4° respectively. In the case of alkylphosphonic acid SAMs (OP, DP, and ODP), the advancing and receding water contact angles increased with an increase in the preparation time. The angle-resolved XPS (AR-XPS) data revealed that the film thicknesses of the OP, DP, ODP, PFEP on Mg alloy were estimated to be 0.8, 1.2, 1.7, and 1.1 nm, respectively. The XPS O 1s data support that the phosphonic acid derived SAM is covalently bound to the oxide or hydroxide surface of the Mg alloy in a monodenate or bidenate manner. Chemical stability of the alkyl- and perfluoro-phosphonic acid modified Mg alloy surfaces was investigated using aqueous solutions at pH=4.0, 7.0, and 10.0. The contact angles of OP, DP, and PFEP modified Mg surface decreased rapidly within the first 5 min after immersion in all the aqueous solutions and were less than 20°. On the other hand, the contact angles of the ODP modified Mg alloy after immersion in aqueous solutions at pH 4, 7 and 10 for 5 min were 45.1°, 89.3,° and 85.5°, respectively. The ODP modified Mg alloy had highest chemical stability in four types of the phosphonic acid derived SAMs used in this study, indicating that the molecular density of ODP on Mg alloy would be higher than those of OP, DP, PFEP on Mg alloy. The corrosion resistance of ODP modified Mg alloy was investigated by potentiodynamic polarization curve measurements. The ODP modified Mg alloy exhibits protective properties in a solution containing Cl(-) ions compared to unmodified Mg alloy.     

Highly shape-selective guest encapsulation in the precisely defined cavity of a calix[4]arene-capped metalloporphyrin

We developed a metalloporphyrin-based molecular container capped with a calix[4]arene, and its rigid cavity distinguished the slight structural differences in the aromatic guests.     

Extended optimal inspection policies for a system in storage

A system such as missiles and spare parts of aircraft has to perform a normal operation in a severe environment at any time when it is used. However, the system is in storage for a long time from the delivery to the usage and its reliability goes down with time. Thus, a system in storage should be inspected and maintained at periodic times to hold a higher reliability than is prespecified.The following inspection model is considered: A system has three types of units, where unit 1 is maintained, unit 21 is not maintained but is replaced and unit 22 is neither maintained nor replaced. The system is overhauled if its reliability becomes lower than a prespecified probability. The number of replacements and time until overhaul are derived. Using these results, the average cost is obtained and both an optimal inspection time and an optimal replacement time to minimize it are numerically discussed.     

Effect of solvent and carbon black species on the rubber–carbon black interactions studied by pulsed NMR

The spin–spin relaxation time T₂ and the fraction of short T₂ component for composites of natural rubber with carbon black prepared under various conditions have been measured by pulsed NMR. Effect of swelling with a solvent (CCl₄), carbon black species (SAF, HAF, SRF) with different surface areas, and different initial carbon black loadings (35, 50, 70 phr) have been determined. Molecular motion in the rubber phase not in the immediate vicinity of the carbon black surface increases rapidly with increasing solvent concentration, yet it is still slightly restricted compared to rubber with solvent alone. On the other hand, molecular motion in the immobilized layer around carbon black and the fraction rubber in that layer are not affected by the solvent. This indicates strong restriction of molecular motion of polymers at the surface. For estimation of the thickness of the immobilized layer, the necessity of using an appropriate measure of surface area accessible to polymer molecules is pointed out. The degree of immobilization in the layer and the thickness of the layer do not vary appreciably with the nature of carbon black or the initial loading of carbon black.     

Kinetics of the phosphorescent triplet states of tetracyanobenzene complexes as studied by microwave induced delayed phosphorescence

Using microwave induced delayed phosphorescence techniques we determined the populating and depopulating rate constants for the individual spin-sublevels of the phosphorescent states of tetracyanobenzene (TCNB) and its charge-transfer complexes with benzene and hexamethylbenzene (HMB) in n-hexane at 1.25 K. It was shown that the non-radiative decay process from the shortest lifetime sublevel is most responsible for the previously observed shortening in the phosphorescence lifetime of the TCNBHMB complex.