Phase morphology development in a low interfacial tension immiscible polyolefin blend during die extrusion and melt spinning

We describe the development of phase morphology in polypropylene (PP)/ethylene–butene copolymer (EBM) blends in both extrusion through dies and in subsequent melt spinning to form filaments. This immiscible blend has a very low interfacial tension around 0.69 dynes/cm. In the die extrusion process, at low extrusion rates, the dispersed PP phase was sheared into fibrils; at higher extrusion rates, the PP fibrils formed an encapsulation layer near the die wall first, then it broke into droplets because of both interfacial tension and long residence time. These droplets agglomerated together to form a network. In melt spinning, the dispersed phase was also drawn down into fibrils, which coalesced into a continuous layer on the outer surface of the filaments at higher drawdown rates. POLYM. ENG. SCI., 50:1969–1977, 2010. © 2010 Society of Plastics Engineers     

Active coke: Carbonaceous materials as catalysts for alkane dehydrogenation

The catalytic dehydrogenation (DH) and oxidative dehydrogenation (ODH) of light alkanes are of significant industrial importance. In this work both carbonaceous material deposited on VO_x/Al₂O₃ catalysts during reaction and unsupported carbon nanofibres (CNFs) are shown to be active for the dehydrogenation of butane in the absence of gas-phase oxygen. Their activity in these reactions is shown to be dependent upon their structure, with different reaction temperatures yielding structurally different coke deposits. Terahertz time-domain spectroscopy (THz-TDS), among other techniques, has been applied to the characterisation of these deposits – the first time this technique has been employed in coke studies. TEM and other techniques show that coke encapsulates the catalyst, preventing access to VO_x sites, without a loss of activity. Studies on CNFs confirm that carbonaceous materials act as catalysts in this reaction. Carbon-based catalysts represent an important new class of potential catalysts for DH and ODH reactions.     

Cloning,Expression and Purification of Cindoxin,an Unusual Fmn‐Containing Cytochrome P450 Redox Partner

Cytochromes P450 (P450s) belong to a superfamily of haemoproteins that catalyse a remarkable variety of oxidative transformations. P450 catalysis generally requires that cognate redox proteins transfer electrons, derived ultimately from NAD(P)H, to the P450 for oxygen activation. P450_cin (CYP176A1) is a bacterial P450 that is postulated to allow Citrobacter braakii to live on cineole as its sole carbon source by initiating cineole biodegradation. Here we report the cloning, expression, purification and characterisation of one of its postulated redox partners, cindoxin (Cdx), which has strong similarity to the FMN domain of cytochrome P450 reductase. Cindoxin reductase (CdR), which displays strong similarity to NADPH‐dependent ferredoxin reductases, was unable to be expressed in a functional form. Mass spectrometric and HPLC analyses confirmed that the flavin cofactor of cindoxin was FMN. Redox potentiometric titrations were performed with cindoxin within the range 6<pH<8; this enabled the quinone/semiquinone (E₁) and semiquinone/hydroquinone (E₂) redox potentials to be determined. Our results show that cindoxin might be somewhat different to other flavodoxins that interact with P450s, in which generally only one couple is important. Both redox states of cindoxin could be catalytically relevant. A catalytically active system was reconstituted in vitro with E. coli flavodoxin reductase (Fpr) acting as the terminal redox partner in the absence of CdR. Our results show that Cdx and Fpr support regio‐ and stereoselective P450_cin‐catalysed cineole oxidation to (1R)‐6β‐hydroxycineole with turnover rates up to 1500 min^?1. This system is tightly coupled with 80 % of NADPH reducing equivalents funnelled into substrate oxidation.     

Generalized hybrid control synthesis for affine systems using sequential adaptive networks

BACKGROUND: A generalized methodology for the synthesis of a hybrid controller for affine systems using sequential adaptive networks (SAN) is presented. SAN consists of an assembly of neural networks that are ordered in a chronological sequence, with one network assigned to each sampling interval. Using a suitable process model based on oxygen metabolism and an a priori objective function, a hybrid control law is derived that can use online measurements and the states predicted by SAN for computing the desired control action. RESULTS: The performance of the SAN–hybrid controller is tested for simulated fed‐batch production of methionine for three different process conditions. Simulations assume that online measurements of dissolved oxygen (DO) concentration are available. The performance of the SAN–hybrid controller gave an NRMSE of ～10^?4 in the absence of noise, ～10^?3 and ～10^?2 for ± 5% and ± 10% noise in the DO measurement and ～10^?2 for parameter uncertainty when compared with the ideal model prediction. CONCLUSIONS: The observed performance for unmeasured state prediction and control implementation shows that the proposed SAN–hybrid controller can efficiently compute the manipulated variable required to maintain methionine production along the optimized trajectory for different conditions. The test results show that the SAN–hybrid controller can be used for online real‐time implementation in fed‐batch bioprocesses. Copyright © 2009 Society of Chemical Industry     

In situ observation of Cu segregation and phase nucleation at a solid–liquid interface in an Al alloy

This paper presents a systematic study comparing experimental in situ transmission electron microscopy observation of microstructural and compositional evolution with complementary thermodynamic calculations, to better understand the redistribution of solute elements and the nucleation behavior of different phases in a commercial Al-alloy powder (AA390). The results show that Cu segregation to the solid Si–liquid Al interface, as well as the significant undercooling achieved in the liquid under non-equilibrium conditions because the Al phase cannot nucleate homogeneously, play a important roles in nucleating Al₂Cu at the interface prior to the Mg₂Si phase in the alloy. Although Cu segregation can occur at various locations along the interface, the Al₂Cu phase appears to preferentially nucleate at a high-index Si–liquid interface as opposed to a low-index one. The Cu concentration during segregation remains essentially constant with time, indicating that the observed segregation behavior is a thermodynamic and not a kinetic phenomenon. These in situ observations and complementary thermodynamic calculations substantially enhance our understanding of potential crystal nucleation and growth processes.     

金刚石钎焊(上)

金刚石磨料主要靠机械夹持力把持在金属(烧结或电镀)胎体中。由于这一弱点,在切割过程中,金刚石不可避免地会从胎体中脱落或掉出。此外,金刚石突出高度较低,故金刚石工具的切割速度受到限制。而且,金属胎体和工作对象(被切割岩石)相互磨擦,将会导致金刚石和其它材料的热损伤,而且工作的功率消耗将增加。金刚石采用钎焊的办法牢固地把持在金属胎体中,可形成强力的化学结合,金刚石磨料的突出高度将成倍提高,而不会从胎体中脱落或碎裂。因此,金刚石工具的切割速度将会成倍提高。当钎焊料熔融时,碳化物形成物将向金刚石方向迁移而在界面上形成碳化物。这种反应可能过分而使金刚石质量明显下降。此时,可能需要对金刚石进行镀覆以便缓和与控制这种反应。当金刚石钎焊在基体的表面时,熔化趋向于将金刚石聚集在一起,可促使钎焊层局部加厚。这种金刚石晶粒的成簇聚集将降低金刚石工具的切割效率。一种金刚石矩阵有序排列设计(grid)是必要的,它可保持钎焊层具有均匀的厚度。因此钎焊合金可控熔融,可使每一粒金刚石晶体周围形成较缓的坡度。这种整体均匀焊层的支承可使金刚石工具高速有效切割,而功率消耗较低。     

Inflammation in the Human Periodontium Induces Downregulation of the α1- and β1-Subunits of the sGC in Cementoclasts

Nitric oxide (NO) binds to soluble guanylyl cyclase (sGC), activates it in a reduced oxidized heme iron state, and generates cyclic Guanosine Monophosphate (cGMP), which results in vasodilatation and inhibition of osteoclast activity. In inflammation, sGC is oxidized and becomes insensitive to NO. NO- and heme-independent activation of sGC requires protein expression of the α₁- and β₁-subunits. Inflammation of the periodontium induces the resorption of cementum by cementoclasts and the resorption of the alveolar bone by osteoclasts, which can lead to tooth loss. As the presence of sGC in cementoclasts is unknown, we investigated the α₁- and β₁-subunits of sGC in cementoclasts of healthy and inflamed human periodontium using double immunostaining for CD68 and cathepsin K and compared the findings with those of osteoclasts from the same sections. In comparison to cementoclasts in the healthy periodontium, cementoclasts under inflammatory conditions showed a decreased staining intensity for both α₁- and β₁-subunits of sGC, indicating reduced protein expression of these subunits. Therefore, pharmacological activation of sGC in inflamed periodontal tissues in an NO- and heme-independent manner could be considered as a new treatment strategy to inhibit cementum resorption.