Ozonation of Two Acidic Azo Dyes with Different Substituents

The ozonation of two differently substituted azo dyes (Schwarz GRS and Orange Acid 8) in water media is studied. The influence of pH on the effectiveness of the ozonation at various initial concentrations of each dye is explored. It was found out that the rates of decolorization for amino-group substituted dyes reflect the considerable influence by the widely varying initial pH from 4.5 to 10. Specifically, the highest effect of decolorization of this dye was obtained at the highest pH studied (pH 10) for all initial concentrations of the solutions. Considering the dye without an amino-group substitute, the rates of color disappearance in ozonation reflected to a lower degree the variations of the initial pH. Pseudo-first-order trends of decolorization were observed in all the experimental runs. Regarding the kinetic results obtained, an attempt to explain the different dyes reactivity was made based on the absolute electronegativity (E_lumo + E_homo) of both dyes. The COD/BOD analysis shows that the ozonation of both azo dyes can reduce the sample COD but it could not improve the biodegradability ratio (BOD₅/COD). BOD decrease with ozonation time indicates that the intermediates of the ozonation are of lower biodegradability. Oxalic acid was found as the final product of ozonation of both dyes.     

Xylose-lysine model systems: The effect of pH on the volatile reaction products

Aqueous molal solutions of xylose and lysine (initial pH 4–9) were refluxed either with control of the pH at 5–0 or without pH control (final pH 2–6). Analysis by gas chromatography (GC) and GC-mass spectrometry resulted in the identification of 58 and 28 compounds, respectively, from the two systems. Furans were the main reaction products in both systems and 2-furfural alone comprised 522 and 999 g kg^?1 of the volatiles, respectively, from the systems with final pH values of 5–0 and 2–6. Maintaining the pH at 5–0 resulted in a higher yield and greater numbers of nitrogen-containing compounds, and monocyclic pyrroles, pyridines and 2,3-dihydro-l H-pyrrolizines were identified only in that system. Aliphatic compounds, alicyclic compounds, benzene derivatives. l-(2–furfuryl)pyrroles and pyrazines were also identified. This investigation is the first report of the formation of 2.3-dihydro-l H-pyrrolizines in a model system containing lysine as the amino compound; a possible mechanism is proposed.     

Optimal synthesis of tunable elastic wave-guides

Topology optimization, or control in the coefficients of partial differential equations, has been successfully utilized for designing wave-guides with precisely tailored functionalities. For many applications it would be desirable to have the possibility of drastically altering the wave-guiding properties of a device “on the fly,” in a controllable manner as an influence of some external input. This would enable wave-guides with highly non-linear input-output mappings, such as for example controllable wave switches.In this paper, we propose using finite elastic pre-straining for the purpose of tuning a wave-guide. In order to systematically formulate and solve the wave-guide synthesis problems we utilize mathematical programming methods in conjunction with topology optimization for parametrizing the design space. The resulting extremal problem is, from a practical point, equivalent to finding an optimal subdivision of a given control volume into two disjoint subsets occupied by two different materials, normally resulting in a highly heterogeneous elastic body with desired wave-guiding functionalities in the original and finitely deformed configurations.The proposed methodology is illustrated with numerical examples.     

State multiplicity in CSTR-separator-recycle polymerisation systems

This article continues earlier work (Comput. Chem. Eng. 24 (2000) 209) concerning the design and control of isothermal reactor-separator-recycle systems. The multiplicity behaviour of six reaction systems of increasing complexity, from one-reactant, first-order reaction to chain-growth polymerisation, is investigated. Below a critical value of the plant Damkohler number, Da<Da^cr, the only steady state involves infinite flow rates. Feasible steady states become possible if the critical value is exceeded, Da>Da^cr. For one-reaction systems, one stable steady state is born at a transcritical bifurcation. For consecutive-reaction systems, including polymerisation, a fold bifurcation can lead to two feasible steady states. Moreover, the transcritical bifurcation is destroyed when two reactants are involved. If the gel-effect is included, a maximum of four steady states are possible. When multiple steady states exist, the achievable conversion is constrained by the instability of the low-conversion branch. This has practical importance for polymerisation systems when the radicals’ quasi-steady state assumption is not valid or the gel effect is significant.     

DMT／PTA工艺的技术改进

改进的DMT/PTA工艺技术是由苏尔寿化工有限公司和H&G Hegmanns公司联合开发的。该技术对Witten-Katzschmann工艺进行了大量改进,并结合了苏尔寿公司的环境友好熔融结晶技术。改进的工艺包括:氧化反应部分(有效回收了副产品和能量);粗酯和副产品蒸馏;采用熔融结晶技术精制DMT。     

Risk evaluations for the courts: Is service quality a function of specialization?

Psychologists are often asked to testify in court. However, concerns have been expressed in both the legal and psychological literatures about the quality of these services. This article presents survey results comparing the practice patterns of generally licensed psychologists with those of specialist forensic diplomates in providing risk evaluations. Results suggest that general clinicians frequently perform these evaluations, but forensic diplomates use more modern risk instruments, are more aware of the scientific literature, and provide the court with more information about the scientific basis of their testimony. The implication of these results for legal professionals, psychologist training, and practice are discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

A Dual-Fed, Self-Diplexing PIFA and RF Front-End

A dual-fed, self-diplexing planar inverted F antenna and an associated RF front-end are described. It is shown that co-design of the antenna and front-end can be used to double the operational bandwidth, without significant size or performance penalties. Indeed, the use of two feeds allows the antenna to be self-diplexing, which results in improved overall efficiency     

Probing the substrate alignment at the active site of 15-lipoxygenases by targeted substrate modification and site-directed mutagenesis. Evidence for an inverse substrate orientation

For oxygenation of polyenoic fatty acids by 12- and 15-lipoxygenases the methyl terminus of the substrate constitutes the signal for the initial hydrogen abstraction. In contrast, for 5-lipoxygenases an inverse head to tail substrate orientation has been proposed. However, recent structure-based sequence alignments suggested a conserved uniform substrate orientation for 5S- and 15S-lipoxygenation. Oxygenation of 15S-HETE derivatives by various wild-type and mutant lipoxygenases was investigated, and the evidence proved an inverse substrate orientation: (i) Substrate affinity and Vmax of 15S-HETE oxygenation by arachidonic acid 15-lipoxygenases are >1 order of magnitude lower than the corresponding data for polyenoic fatty acids. 5S,15S- and 14R, 15S-DiH(P)ETE were identified as major reaction products. (ii) Methylation of the carboxylate group of 15S-HETE augmented the reaction rate and shifted the reaction specificity strongly toward 5S-lipoxygenation. In contrast, methyl arachidonate was less effectively oxygenated than the free acid. Methylation of 15S-HETrE(8,11,14), which lacks the C5-C6 double bond, was without major impact on the oxygenation rate and on the product specificity. (iii) Introduction of a bulky glycerol moiety at the carboxylic group of 15S-HETE reversed the kinetic effects of methylation and led to a 14R-oxygenation of the substrate. (iv) When the product pattern of 15S-HETE oxygenation by the recombinant wild-type rabbit 15-lipoxygenase was compared with that formed by the Arg403Leu mutant, 5S- and 8S-lipoxygenations were augmented and 14R, 15S-DiH(P)ETE formation was impaired. (v) Phe353Leu or Ile418Ala mutation of the same enzyme, which favored 12S-HETE formation from arachidonic acid, strongly augmented 8S-lipoxygenation of 15S-HETE methyl ester. These kinetic data and the alterations in the product specificity are consistent with the concept of an inverse head to tail substrate orientation during the oxygenation of 15S-HETE methyl ester and/or of free 15S-HETE by 15-LOXs. For 5S- and 8S-lipoxygenation, 15-HETE may slide into the substrate binding pocket with its carboxy terminus approaching the doubly allylic methylenes C-7 or C-10 to the non-heme iron.     

Cathepsin L2, a novel human cysteine proteinase produced by breast and colorectal carcinomas

We have identified and cloned a new member of the papain family of cysteine proteinases from a human brain cDNA library. The isolated cDNA codes for a polypeptide of 334 amino acids that exhibits all of the structural features characteristic of cysteine proteinases, including the active site cysteine residue essential for peptide hydrolysis. Pairwise comparisons of this amino acid sequence with the remaining human cysteine proteinases identified to date showed a high percentage of identity (78%) with cathepsin L; the percentage of identity with all other members of the family was much lower (<40%). On the basis of these structural characteristics, we have tentatively called this novel protein cathepsin L2. The cDNA encoding the mature cathepsin L2 was expressed in Escherichia coli, and after purification, the recombinant protein was able to degrade the synthetic peptide benzyloxycarbonyl-L-phenylalanyl-L-arginine-7-amido-4-methylcoumarin, which is commonly used as a substrate for cysteine proteinases. Cathepsin L2 proteolytic activity on this substrate was abolished by trans-epoxysuccinyl-L-leucylamido-(4-guanidino)butane, an inhibitor of cysteine proteinases, thus providing additional evidence that the isolated cDNA encodes a functional cysteine proteinase. Northern blot analysis of polyadenylated RNAs isolated from a variety of human tissues demonstrated that cathepsin L2 is predominantly expressed in the thymus and testis. This finding is in marked contrast with the wide tissue distribution of most cysteine proteinases characterized to date, including cathepsin L, and suggests that cathepsin L2 may play a specialized role in the thymus and testis. Expression analysis of cathepsin L2 in human tumors revealed a widespread expression in colorectal and breast carcinomas but not in normal colon or mammary gland or in peritumoral tissues. Cathepsin L2 was also expressed by colorectal and breast cancer cell lines as well as by some tumors of diverse origin, including ovarian and renal carcinomas. These results open the possibility that this novel enzyme may be involved in tumor processes, as already reported for other cysteine proteinases, including cathepsin L.