Synthesis,characterization and compared reactivity of asymmetrical ansa-metallocenes

Rac and meso ansa-zirconocenes [Zr{1-Me₂Si(3-R-(η⁵-C₉H₅))(3-R′-(η⁵-C₉H₅))}Cl₂] (R = Et, R′ = H; R = Pr, R′ = H; and R = Et, R′ = Pr) 4–9 have been prepared by the reaction of ZrCl₄ with the corresponding dilithiated derivatives from the ligands {1-Me₂Si(3-R-(η⁵-C₉H₅))(3-R′-(η⁵-C₉H₅))} (R = Et, R′ = H 1; R = Pr, R′ = H 2; and R = Et, R′ = Pr 3) in diethyl ether/toluene at ?78 °C. The molecular structure of rac [Zr{1-Me₂Si(3-Et-(η⁵-C₉H₅))(3-Pr-(η⁵-C₉H₅))}Cl₂] 8 has been determined by single crystal X-ray diffraction studies, which show a pseudotetrahedral environment formed by the two chlorine ligands and two η⁵-coordinated indenyl ligands. The activity in homogeneous and heterogeneous polymerization is compared and discussed.     

Modification with Organometallic Compounds Improves Crossing of the Blood–Brain Barrier of [Leu5]‐Enkephalin Derivatives in an In Vitro Model System

Enkephalin peptides are thought to be suitable vectors for the passage of the blood–brain barrier (BBB). Modifications that do not alter the amino acid sequence are often used to improve the permeation through living membrane systems. As a new type of modification we introduce organometallic compounds, in particular ferrocene carboxylic acid. Derivatives of [Leu⁵]enkephalin were synthesised and labelled with organometallic compounds by using solid‐phase synthesis techniques. All new metal–peptide bioconjugates were comprehensively characterised by HPLC, NMR spectroscopy and mass spectrometry and found to be at least 95 % pure. For the first time, permeation coefficients in a BBB model for organometal–peptide derivatives were determined in this work. The uptake and localisation of fluorescein‐labelled enkephalins was monitored by fluorescence microscopy on three cancer cell lines. Octanol/H₂O partition coefficients of the compounds were measured by HPLC. The introduction of the organometallic moiety enhances the uptake into cells and the permeation coefficient of [Leu⁵]‐enkephalin. This could be due to an increase in lipophilicity caused by the organometallic label. The metal–peptide conjugates were found to be nontoxic up to mM concentrations. The low cytotoxicity encourages further experiments that could take advantage of the selectivity of enkephalin derivatives for opioid receptors.     

Combined Treatment with Dif1stat<Superscript>®</Superscript> and Diet Reduce Plasma Lipid Indicators of Moderate Hypercholesterolemia More Effectively than Diet Alone: A Randomized Trial in Parallel Groups

An open-labeled randomized trial with parallel groups was carried out to study the effects of Dif1stat^® (Monascus purpureus–Linear aliphatic alcohols–Niacin) in the treatment of primary moderate hypercholesterolemia. The trial lasted 8 months. The patients, males and females, were assigned to two groups: A (#130), treated with diet, and B (#110) submitted to diet + Dif1stat^®. After 4 months, group A did not show significant changes in Total cholesterol (TC), LDL-cholesterol (LDLC), HDL-cholesterol (HDLC) or non-HDL-cholesterol (non-HDLC). The same group, showed a reduction in TC (–22%), LDLC (–30%) and non-HDLC (–27%) after 8 months (P ≤ 0.001). After 4 months, TC (–21.3%), LDLC (–29%), and non-HDLC (–26%) were significantly lowered in group B (P ≤ 0.001). In group B, TC, LDLC and non-HDLC showed a further reduction after 8 months: –29.4, –38 and –37%, respectively (P ≤ 0.001). Even triglycerides (TG) decreased significantly (–33%) (P ≤ 0.001). After 8 months, group B showed a significant reduction of TG (–33%) (P ≤ 0.001), when compared to group A. Some safety parameters were significantly reduced in both groups: AST and γ-GT in group A after 4 and 8 months, as well as ALT, AST and γ-GT in group B after 8 months (P ≤ 0.001). Dif1stat^®, given with a suitable diet, was well tolerated in the long-term and induced an anti-atherogenic plasma lipid and lipoprotein profile, in patients with moderate hypercholesterolemia.     

Arch-Free flow in aerated silo discharge of cohesive powders

Arching can occur during silo discharge of cohesive powders. In general this happens when the outlet size is not wide enough. Flow aid devices, such as aeration pads, are commonly used in the industry to achieve proper flow of cohesive materials. However, no design criteria are presently available for such kind of devices and, in particular, for the intensity of aeration to be used to avoid arching. Aim of this paper is the evaluation of the limiting aeration condition to produce the collapse of established arches and the minimum aeration rate necessary for no arching discharge flow. Experimental tests are carried out in an aerated flat bottom silo. The measured quantities are the aeration rate at arch collapse and the arch size. Powder permeability is characterized by fluidization experiments. A simplified model is proposed to assess on the prevailing physical phenomena and predictively evaluate the minimum aeration rate to determine no arching discharge flow.     

Incorporating environmental impacts and regulations in a holistic supply chains modeling: An LCA approach

Corporate approaches to improve environmental performance cannot be undertaken in isolation, so a concerted effort along the supply chain (SC) entities is needed which poses another important challenge to managers. This work addresses the optimization of SC planning and design considering economical and environmental issues. The strategic decisions considered in the model are facility location, processing technology selection and production–distribution planning. A life cycle assessment (LCA) approach is envisaged to incorporate the environmental aspects of the model. IMPACT 2002+ methodology is selected to perform the impact assessment within the SC thus providing a feasible implementation of a combined midpoint–endpoint evaluation. The proposed approach reduces the value-subjectivity inherent to the assignment of weights in the calculation of an overall environmental impact by considering endpoint damage categories as objective function. Additionally, the model performs an impact mapping along the comprising SC nodes and activities. Such mapping allows to focus financial efforts to reduce environmental burdens to the most promising subjects. Furthermore, consideration of CO₂ trading scheme and temporal distribution of environmental interventions are also included with the intention of providing a tool that may be utilized to evaluate current regulatory policies or pursue more effective ones. The mathematical formulation of this problem becomes a multi-objective MILP (moMILP). Criteria selected for the objective function are damage categories impacts, overall impact factor and net present value (NPV). Main advantages of this model are highlighted through a realistic case study of maleic anhydride SC production and distribution network.     

Bisorbicillinoids Produced by the Fungus <Emphasis Type="Italic">Trichoderma citrinoviride</Emphasis> Affect Feeding Preference of the Aphid <Emphasis Type="Italic">Schizaphis graminum</Emphasis>

We report the effects of some bisorbicillinoids isolated from biomass of the fungus Trichoderma citrinoviride on settling and feeding preference of the aphid Schizaphis graminum. Purification of the fungal metabolites was carried out by a combination of column chromatography and thin-layer chromatography using direct and reverse phases. Chemical identification was performed by spectroscopic methods including nuclear magnetic resonance and mass spectrometry. The identified bisorbicillinoids appeared to be bislongiquinolide, its 16,17-dihydro derivative, trichodimerol, and dihydrotrichodimerol. A feeding preference test with alate morphs of S. graminum was used to identify the active fractions. Among the four bisorbicillinoids, dihydrotrichodimerol and bislongiquinolide influenced aphid feeding preference, restraining specimens from settling on leaves treated with metabolites. Taste neurons sensitive to these compounds, particularly to bislongiquinolide, were located on tarsi of the S. graminum alate morphs.     

Blue pigments based on CoxZn1−xAl2O4 spinels synthesized by the polymeric precursor method

The Co_xZn_1?xAl₂O₄ system (x = 0; 0.1; 0.3; 0.5; 0.7; 0.9 and 1) was synthesized by the polymeric precursor method and characterized by the techniques XRD, TG-DTA, IR, UV–vis and colorimetry. The XRD patterns displayed the characteristic peaks of the spinel structure and a good crystallinity. The DTA curves showed an exothermic peak corresponding to the enthalpy of the transition taking place at about 700 °C. The infrared spectra displayed vibrations at about 650, 550, 540, 520, 500, 490 cm^?1, which were ascribed to the spinel structure. The UV–vis spectra presented three bands at 550, 580 and 620 nm attributed to the Co²⁺ spin transitions in tetrahedral sites. The colorimetric data point out the formation of blue pigments, corresponding to highly negative values of b¹. The lightness, coordinate L¹, increases with the heat treatment temperature. These facts reveal that Co_xZn_1?xAl₂O₄ is a promising system that can be employed to obtain ceramic blue pigments.     

Design optimization of twin-fluid atomizers with an internal mixing chamber for heavy fuel oils

The present work is devoted to determine the magnitude of the main parameters that yield the optimum results for twin-fluid nozzles with an internal mixing chamber. The focus is placed on the study of the interaction of both air and liquid flows at the internal chamber and its effects on the resulting spray. To this end, some experiments have been performed for different air central channel diameters and liquid ports, as well as for several experimental conditions (air and liquid mass flow rates), in order to understand the influence of the flow conditions at the mixing chamber on the size of the droplets produced. It has been demonstrated that under certain experimental conditions the atomizing fluid discharged to the internal chamber is choked. The sonic condition is achieved for different air and liquid mass flow rates as a function of the air central channel diameter. It has also been obtained that to achieve the best results with moderate atomizing fluid flow rates, it is convenient to operate in choked conditions. This is an important result that will help in the optimum design of this type of nozzles.     

Dislocations at Prismatic Fracture Surfaces in Sapphire

Single-crystal sapphire exhibits a highly anisotropic fracture behavior. The surfaces of specimens fractured along prismatic planes are wavy, with fractographic features appearing as small areas of contrast under an optical microscope. Optical microscopy, atomic force microscopy, X-ray topography, and confocal microscopy are used to demonstrate a correlation between the areas of contrast and dislocations penetrating the sample surface. The surface features are argued to be a consequence of the stress field surrounding the dislocations, which deflect the crack approximately 10 nm normal to the surface as the crack cuts the dislocations. The lateral extent of measurable surface deflection is of the order of 5 μm. These images can be compared directly to show the equivalence of the position of the dislocations observed by X-ray topography and the surface contrast observed optically.     

A neural network approach to predict activity coefficients

Artificial neural networks (ANNs) and a group‐contribution approach were used to develop an algorithm to predict activity coefficients for binary solutions. The Levenberg–Marquardt algorithm was used to train the ANN and to predict the parameters of the Margules equation. The ANN was trained using phase‐equilibrium database from DECHEMA. The selected systems include alcohols, phenols, aldehydes, ketones, and ethers. The trim mean based on 20% data elimination was selected as the best representation of the Margules‐equation parameters. The algorithm was validated with 121 VLE systems and results show that the ANN provides a relative improvement over the UNIFAC method.