Complete filling of zeolite frameworks with polyalkynes formed in situ by transition-metal ion catalysts

We report the use of transition-metal-exchanged zeolites as media for the catalytic formation and encapsulation of both polyethyne and polypropyne, and computer modeling studies on the composites so formed. Alkyne gas was absorbed into the pores of zeolite Y (Faujasite) exchanged with transition-metal cations [Fe(II), Co(II), Cu(II), Ni(II), and Zn(II)]. Ni(II) and Zn(II) were found to be the most efficient for the production of poly-ynes. These cations were also found to be effective in polymer generation when exchanged in zeolites mordenite and beta. The resulting powdered samples were characterized by FTIR, Raman, diffuse reflectance electronic spectroscopy, TEM, and elemental analysis, revealing, nearly complete loading of the zeolite channels for the majority of the samples. Based on the experimental carbon content, we have derived the percentage of channel filling, and the proportion of the channels containing a single polymer chain for mordenite. Experimentally, the channels for Y are close to complete filling for polyethyne (PE) and polypropyne (PP), and this is also true for polyethyne in mordenite. Computer modeling studies using Cerius2 show that the channels of mordenite can only accept a single polymer chain of PP, in which case these channels are also completely filled.

Cascade dicopper architectures of a dibenzodioxatetraazamacrocycle

The dibenzodioxatetraazamacrocycle [26]pbz(2)N(4)O(2) was characterised by single crystal X-ray diffraction and the protonation constants of this compound and the stability constants of its copper(II) and lead(II) complexes were determined by potentiometry in water at 298.2 K in 0.10 mol dm(-3) in KNO3. Mono- and dinuclear complexes were found for both metal ions, the dinuclear complexes being the main species in the 5-7.5 pH range for copper(II) and 7.5-8.5 for lead(II). As expected the values of the stability constants for the copper(II) complexes are lower than those for related macrocycles containing only nitrogen atoms. The presence of mono- and dinuclear copper complexes was also confirmed by electrospray ionization mass spectrometry. These results suggest that the symmetric macrocyclic cavity of [26]pbZ(2)N(4)O(2) has enough space for the coordination of two metal ions. Additionally, NMR spectroscopy showed that the dinuclear complex of lead(II) has high symmetry. The equilibrium constants of the dinuclear copper(II) complexes and dicarboxylate anions (oxalate, malonate and succinate) were also determined in 0.10 mol dm-3 aqueous KNO3 solution. Only species containing one anion, Cu(2)H(h)LA((2+h)), were found, strongly suggesting that the anion bridges the two copper(II) ions. The binding constants of the cascade species formed by [Cu-2[26]pbZ(2)N(4)O(2)(H2O)(4+) with dicarboxylate anions decrease with the increase in length of the alkyl chain of the anion, a fact which was attributed to a higher conformational energy necessary for the rearrangement of the macrocycle to accommodate the larger anions bridging the two copper(II) centres. The variation of the magnetic susceptibility with temperature Of [Cu-2(H-2[26]pbz(2)N(4)O(2))(oxa)(3)]-4H(2)O and [Cu-2([26]pbz(2)N(4)O(2))(suc)Cl-2] were measured and the two complexes showed different behaviour. (c) 2007 Elsevier Ltd. All rights reserved.

The component polypeptide chains of bovine insulin nucleate or inhibit aggregation of the parent protein in a conformation-dependent manner

Amyloid fibrils are typically rigid, unbrariched structures with diameters of similar to 10 nm and lengths up to several micrometres, and are associated with more than 20 diseases including Alzheimer's disease and type II diabetes. Insulin is a small, predominantly alpha-helical protein consisting of 51 residues in two disulfide-linked polypeptide chains that readily assembles into amyloid fibrils under conditions of low PH and elevated temperature. We demonstrate here that both the A-chain and the B-chain of insulin are capable of forming amyloid fibrils in isolation under similar conditions, with fibrillar morphologies that differ from those composed of intact insulin. Both the A-chain and B-chain fibrils were found to be able to cross-seed the fibrillization of the parent protein, although these reactions were substantially less efficient than self-seeding with fibrils composed of full-length insulin. In both cases, the cross-seeded fibrils were morphologically distinct from the seeding, material, but shared common characteristics with typical insulin fibrils, including a very similar helical repeat. The broader distribution of heights of the cross-seeded fibrils compared to typical insulin fibrils, however, indicates that their underling protofilament hierarchy may be subtly different. In addition, and remarkably in view of this seeding behavior, the soluble forms of the A-chain and B-chain peptides were found to be capable of inhibiting insulin fibril formation. Studies using mass spectrometry suggest that this behavior might be attributable to complex formation between insulin and the A-chain and B-chain peptides. The finding that the same chemical form of a polypeptide chain in different physical states can either stimulate or inhibit the conversion of a protein into amyloid fibrils sheds new light on the mechanisms underlying fibril formation, fibril strain propagation and amyloid disease initiation and progression. (c) 2006 Elsevier Ltd. All rights reserved.

Syntheses and crystal structures of two new coordination polymers of Cd(II) using organic spacer and inorganic-bridging ligands

Two new cadmium (II) complexes [Cd(hmt)(dca)(2)] (n) (1) and [Cd-3(hmt)(2)(SeCN)(6)(H2O)(2)] (n) (2) (hmt=hexamethylenetetramine, dca=dicyanamide) have been synthesized and characterized by X-ray single-crystal analysis. The complex 1 is a 2D rectangular grid of octahedral cadmium (II) with CdN6 chromophore where cadmium centers are doubly bridged by dicyanamide and hmt along a-axis, which are interlinked by dicyanamide running along c-axis. Whereas, complex 2 is a 1D chain of octahedral cadmium (II) with a three-leg ladder topology running along a-axis. The Cd(II) centers are doubly bridged through SeCN (infinite rail) along a-axis and singly bridged by hmt (two-step rung) along c-axis, having cadmium centers with CdSe2N3O and CdSe2N4 chromophores. The adjacent chains through H-bonding between coordinated water and hmt, and (SeSe)-Se-... interaction are extended to 2D supramolecular architecture.

Rovibrational energy levels for the electronic ground state of A1OH

The vibrational-rotational energy levels of aluminum monohydroxide in its electronic ground state, (A) over tilde (1)A' AlOH, have been predicted using the variational method. The potential energy surface of the (X) over tilde (1)A' ground state of AlOH was determined employing the ab initio coupled cluster method with single, double, and perturbative triple excitations [CCSD(T)] and the correlation-consistent polarized valence quadruple zeta (cc-pVQZ) basis set. Low-lying J= 0 and J= 1 vibrational levels are reported. These are analyzed in terms of the quasilinearity of the molecule. Coriolis effects are shown to be significant. We hope that our predictions will be of value in the future when assigning rovibrational transitions in spectroscopic studies. (c) 2006 Elsevier B.V. All rights reserved.

Cu-II acetate complexes involving N,N,O donor Schiff base ligands: Mono-atomic oxygen bridged dimers and alternating chains of the dimers and Cu-2(OAc)(4)

Two tridentate N,N,O donor Schiff bases, HL1 (4-(2-ethylamino-ethylimino)-pentan-2-one) and HL2 (3-(2-amino-propylimino)-1-phenyl-butan-1-one) on reaction with Cu-II acetate in presence of triethyl amine yielded two basal-apical, mono-atomic acetate oxygen-bridging dimeric copper(II) complexes, [Cu2L21(OAc)(2)] (1), [Cu2L22(OAc)(2)] (2). Whereas two other similar tridentate ligands HL3 (4-(2-amino-propylimino)-pentane-2-one) and HL3 (3-(2-amino-ethylimino)-1-phenyl-butan-1-one) under the same conditions produced a mixture of the corresponding dinners and a one-dimensional alternating chain of the dimer and copper acetate moiety, [Cu4L23(OAc)(6)](n) (3) and [Cu4L24(OAc)(6)](n) (4), formed by a very rare mu(3) bridging mode of the acetate ion. All four complexes (1-4) have been characterized by X-ray crystallography. The isotropic Hamiltonian, H = -JS(1)S(2) has been used to interpret the magnetic data. Magnetic measurements of 1 and 2 in the temperature range 2-300 K reveal a very weak antiferromagnetic coupling for both complexes U = -0.56 and -1.19 cm(-1) for 1 and 2, respectively). (C) 2008 Elsevier Ltd. All rights reserved.

High value information in engineering organisations

The management of information in engineering organisations is facing a particular challenge in the ever-increasing volume of information. It has been recognised that an effective methodology is required to evaluate information in order to avoid information overload and to retain the right information for reuse. By using, as a starting point, a number of the current tools and techniques which attempt to obtain ‘the value’ of information, it is proposed that an assessment or filter mechanism for information is needed to be developed. This paper addresses this issue firstly by briefly reviewing the information overload problem, the definition of value, and related research work on the value of information in various areas. Then a “characteristic” based framework of information evaluation is introduced using the key characteristics identified from related work as an example. A Bayesian Network diagram method is introduced to the framework to build the linkage between the characteristics and information value in order to quantitatively calculate the quality and value of information. The training and verification process for the model is then described using 60 real engineering documents as a sample. The model gives a reasonable accurate result and the differences between the model calculation and training judgements are summarised as the potential causes are discussed. Finally, several further issues including the challenge of the framework and the implementations of this evaluation assessment method are raised.

Gene transcription in Daphnia magna: effects of acute exposure to a carbamate insecticide and an acetanilide herbicide.

Daphnia magna is a key invertebrate in the freshwater environment and is used widely as a model in ecotoxicological measurements and risk assessment. Understanding the genomic responses of D. magna to chemical challenges will be of value to regulatory authorities worldwide. Here we exposed D. magna to the insecticide methomyl and the herbicide propanil to compare phenotypic effects with changes in mRNA expression levels. Both pesticides are found in drainage ditches and surface water bodies standing adjacent to crops. Methomyl, a carbamate insecticide widely used in agriculture, inhibits acetylcholinesterase, a key enzyme in nerve transmission. Propanil, an acetanilide herbicide, is used to control grass and broad-leaf weeds. The phenotypic effects of single doses of each chemical were evaluated using a standard immobilisation assay. Immobilisation was linked to global mRNA expression levels using the previously estimated 48h-EC(1)s, followed by hybridization to a cDNA microarray with more than 13,000 redundant cDNA clones representing >5000 unique genes. Following exposure to methomyl and propanil, differential expression was found for 624 and 551 cDNAs, respectively (one-way ANOVA with Bonferroni correction, Pof genes involved in specific processes such as ion homeostasis and xenobiotic metabolism. Propanil highly promoted haemoglobin synthesis and up-regulated genes specifically related to defence mechanisms (e.g., innate immunity response systems) and neuronal pathways. Pesticide-specific toxic responses were found but there is little evidence for transcriptional responses purely restricted to genes associated with the pesticide target site or mechanism of toxicity.

The value premium and time-varying volatility

Numerous studies have documented the failure of the static and conditional capital asset pricing models to explain the difference in returns between value and growth stocks. This paper examines the post-1963 value premium by employing a model that captures the time-varying total risk of the value-minus-growth portfolios. Our results show that the time-series of value premia is strongly and positively correlated with its volatility. This conclusion is robust to the criterion used to sort stocks into value and growth portfolios and to the country under review (the US and the UK). Our paper is consistent with evidence on the possible role of idiosyncratic risk in explaining equity returns, and also with a separate strand of literature concerning the relative lack of reversibility of value firms' investment decisions.

New high technology product development: The case of light emitting diodes

New high technology products usher in novel possibilities to transform the design, production and use of buildings. The high technology companies which design, develop and introduce these new products by generating and applying novel scientific and technical knowledge are faced with significant market uncertainty, technological uncertainty and competitive volatility. These characteristics present unique innovation challenges compared to low- and medium technology companies. This paper reports on an ongoing Construction Knowledge Exchange funded project which is tracking, real time, the new product development process of a new family of light emitting diode (LEDs) technologies. LEDs offer significant functional and environmental performance improvements over incumbent tungsten and halogen lamps. Hitherto, the use of energy efficient, low maintenance LEDs has been constrained by technical limitations. Rapid improvements in basic science and technology mean that for the first time LEDs can provide realistic general and accent lighting solutions. Interim results will be presented on the complex, emergent new high technology product development processes which are being revealed by the integrated supply chain of a LED module manufacture, a luminaire (light fitting) manufacture and end user involved in the project.

Farm animal welfare, consumer willingness to pay, and trust: results of a cross-national survey

Higher animal welfare standards increase costs along the supply chain of certified animal-friendly products (AFP). Since the market outcome of certified AFP depends on consumer confidence toward supply chain operators complying with these standards, the role of trust in consumer willingness-to-pay (WTP) for AFP is paramount. Results from a contingent valuation survey administered in five European Union countries show that WTP estimates were sensitive to robust measures of consumer trust for certified AFP. Deriving the WTP effect of a single food category on total food expenditure is difficult for survey respondents; hence, a budget approach was employed to facilitate this process.

Drivers of fund performance: a panel data analysis

The principle aim of this research is to elucidate the factors driving the total rate of return of non-listed funds using a panel data analytical framework. In line with previous results, we find that core funds exhibit lower yet more stable returns than value-added and, in particular, opportunistic funds, both cross-sectionally and over time. After taking into account overall market exposure, as measured by weighted market returns, the excess returns of value-added and opportunity funds are likely to stem from: high leverage, high exposure to development, active asset management and investment in specialized property sectors. A random effects estimation of the panel data model largely confirms the findings obtained from the fixed effects model. Again, the country and sector property effect shows the strongest significance in explaining total returns. The stock market variable is negative which hints at switching effects between competing asset classes. For opportunity funds, on average, the returns attributable to gearing are three times higher than those for value added funds and over five times higher than for core funds. Overall, there is relatively strong evidence indicating that country and sector allocation, style, gearing and fund size combinations impact on the performance of unlisted real estate funds.

Detection of faults in a high speed packaging machine using a multilayer perceptron (MLP)

In high speed manufacturing systems, continuous operation is desirable, with minimal disruption for repairs and service. An intelligent diagnostic monitoring system, designed to detect developing faults before catastrophic failure, or prior to undesirable reduction in output quality, is a good means of achieving this. Artificial neural networks have already been found to be of value in fault diagnosis of machinery. The aim here is to provide a system capable of detecting a number of faults, in order that maintenance can be scheduled in advance of sudden failure, and to reduce the necessity to replace parts at intervals based on mean time between failures. Instead, parts will need to be replaced only when necessary. Analysis of control information in the form of position error data from two servomotors is described.