Torque‐rheometry investigation of model transreactions involving condensation polymers. I. Polyesters

The chemical transformations taking place when poly(ethylene terephthalate) (PET) or poly(ethylene naphthalate) (PEN) are blended in the melt with different low molar mass substances containing hydroxyl, carboxyl, or amine functional groups have been investigated as models of the transreactions, undergone by the polyesters in reactive blending operations. The polyester molecular weight changes caused by the alcoholysis, acidolysis, aminolysis, and esterolysis reactions have been monitored by torque‐rheometry, using a Brabender Plasticorder static mixer. The degradation of the polyesters by hydrolysis was also studied, under similar conditions, by the addition of a water‐releasing substance (wet polyamide‐6), and was shown to occur quite rapidly, although most of the added water was lost by flash vaporization caused by the high temperature of the polyester melt. It has been shown that the rate constants of the reactions leading to breakage of the inner ester bonds of the polyester macromolecules decrease in the following order: aminolysis (with aliphatic amines, either primary and secondary) > alcoholysis (with aliphatic alcohols) ≈ hydrolysis > acidolysis (with aromatic acids) ≥ acidolysis (with aliphatic acids) ? aminolysis (with aromatic amines) > alcoholysis (with phenols) ? esterolysis. POLYM. ENG. SCI. 46:139–152, 2006. © 2005 Society of Plastics Engineers     

Cogeneration plant in a pasta factory: Energy saving and environmental benefit

Italy produces approximately 4,520,000 tons of pasta annually, which is about 67% of its total productive potential. As factories need electric and thermal energy simultaneously, combined heat and power (CHP) systems are the most suitable. This paper describes a feasibility study of a CHP plant in a pasta factory in Italy while analyzing energy saving and environmental benefits. Commercially available CHP systems suitable for the power range of energy demand in pasta production use reciprocating engines or gas turbines. This study demonstrates how their use can reduce both energy costs and CO₂ equivalent greenhouse gas emission in the environment. An economic analysis was performed following the methodology set out by Italian National Agency for Technology, Energy and Environment (ENEA) based on a discounted cash flow (DCF) method called “Valore Attuale Netto” (VAN), which uses a cash flow based on the saving of energy when using different energy processes.     

Treatment of paper and pulp wastewater and removal of odorous compounds by a Fenton‐like process at the pilot scale

A Fenton‐like process, involving oxidation and coagulation, was evaluated for the removal of odorous compounds and treatment of a pulp and paper wastewater. The main parameters that govern the complex reactive system [pH and Fe(III) and hydrogen peroxide concentrations] were studied. Concentrations of Fe(III) between 100 and 1000 mg L^?1 and of H₂O₂ between 0 and 2000 mg L^?1 were chosen. The main mechanism for color removal was coagulation. The maximum COD, color and aromatic compound removals were 75, 98 and 95%, respectively, under optimal operating conditions ([Fe(III)] = 400 mg L^?1; [H₂O₂] = 500–1000 mg L^?1; pH = 2.5; followed by coagulation at pH 5.0). The biodegradability of the wastewater treated increased from 0.4 to 0.7 under optimal conditions and no residual hydrogen peroxide was found after treatment. However, partially or non‐oxidized compounds present in the treated wastewater presented higher acute toxicity to Artemia salina than the untreated wastewater. Based on the optimum conditions, pilot‐scale experiments were conducted and revealed a high efficiency in relation to the mineralization of organic compounds. Terpenes [(1S)‐α‐pinene, β‐pinene, (1R)‐α‐pinene and limonene] were identified in the wastewater and were completely eliminated by the Fenton‐like treatment. Copyright © 2006 Society of Chemical Industry     

Pyrolysis Kinetics for the Conversion of a Polymer into an Amorphous Silicon Oxycarbide Ceramic

We present experimental and analytical results for the pyrolysis reactions underlying the conversion of a cross-linked polymer into an amorphous ceramic material. The activation energies, obtained from thermogravimetric data, and chemical analysis of the volatiles by mass spectroscopy are used to identify the reaction pathways. The reaction is determined to be first-order, which is consistent with its solid-state nature. The magnitude of the weight loss is analyzed to calculate the number of molecular sites in the polymer that participate in the reaction. The experiments were conducted on a polymer made from silsesquioxanes that convert into silicon oxycarbide ceramics on pyrolysis. The results show that <2.5% of the silicon atoms in the polymer are removed as volatile silanes, and less than one-half of the carbon atoms are lost as methane. These results are a first step in understanding the molecular basis for the ceramic yield, as well as the evolution of the nanostructure as the material changes from an organic into a ceramic state by reactions that can occur at <850°C.     

Mixtures of cyclic oligomers of poly(lactic acid) analyzed by negative chemical lonization and thermospray mass spectrometry

Summary An investigation of the distribution of the cyclic oligomers of poly(lactic acid), formed both by pyrolysis of the polymer and by equilibration with a catalyst, has been performed by Negative Chemical Ionization and Thermospray Mass Spectrometry.The results indicate that the two methods can be used to obtain information on the relative amounts of the oligomers present in the mixture.     

Input-Output Equivalence of Spin Networks under Multiple Measurements

Two quantum control systems that are driven by an external field are said to be input–output equivalent if, for any control field, the measured value of a given observable is the same. Equivalent models cannot be distinguished by experiments involving state evolutions and measurements. In this paper, we characterize the equivalent models of networks of spin driven by electro-magnetic fields for which the expectation value of the total magnetization is measured. Extending previous results and definitions that only dealt with the case of a single measurement, we describe the class of equivalent models under a sequence of Von Neumann measurements. The results are motivated by the problem of parameter identification for Heisenberg spin systems modeling molecular magnets.Mathematics Subject Classifications (2000): 93B30, 17B45, 17B81Partially supported by M.I.U.R., project Viscosity, metric, and control theoretic methods for nonlinear partial differential equations.Supported by NSF Career Grant, ECS0237925.     

Microvascular growth, development, and remodeling in the embryonic avian kidney: the interplay between sprouting and intussusceptive angiogenic mechanisms

Embryonic development is associated with extensive vascular growth and remodeling. We used immunohistochemical, light and electron microscopical techniques, as well as vascular casting methods to study the developing chick embryo kidney with special attention to the interplay between sprouting and intussusceptive vascular growth modes. During inauguration at embryonic day 5 (E5), the early mesonephros was characterised by extensive microvascular sprouting. By E7, the vascular growth mode switched to intussusception, which contributed to rapid kidney vasculature growth up to E11, when the first obvious signs of vascular degeneration were evident. The metanephros underwent similar phases of vascular development inaugurating at E8 with numerous capillary sprouts and changing at E13 to intussusceptive growth, which was responsible for vascular amplification and remodeling. A phenomenal finding was that future renal lobules arose as large glomerular tufts, supplied by large vessels, which were split into smaller intralobular feeding and draining vessels with subsequent formation of solitary glomeruli. This glomerular duplication was achieved by intussusception, i.e., by formation of pillars in rows and their successive merging to delineate the vascular entities. Ultimately, the maturation of the vasculature was achieved by intussusceptive pruning and branching remodeling. An interesting finding was that strong VEGF expression was associated with the sprouting phase of angiogenesis while bFGF was upregulated during the phase of intussusceptive microvascular growth. We conclude that microvascular growth and remodeling in avian kidney follows an adroitly crafted pattern, which entails a precise spaciotemporal interplay between sprouting and intussusceptive angiogenic growth modes supported partly by VEGF and bFGF.     

Bowman-Birk inhibitors in lentil: Heterologous expression,functional characterisation and anti-proliferative properties in human colon cancer cells

A full-length cDNA, encoding a Bowman-Birk protease inhibitor (BBI), was isolated from lentil immature seeds. The deduced amino acid sequence was longer than that of the BBI extracted from lentil seeds and contained two binding sites; the first inhibitory site inhibits trypsin whereas the second one inhibits chymotrypsin. In order to characterize this lentil BBI, a longer (complete) and its C-terminally processed (mature) form were heterologously expressed in the yeast Pichia pastoris. The recombinant BBI proteins proved to be active against trypsin and chymotrypsin, showing K_i values at nanomolar levels. Mass spectrometry analysis revealed that complete BBI was composed of an array of molecular masses, whereas mature BBI showed the presence of a major peak of the expected size. The effects of mature BBI on the growth of human colon adenocarcinoma HT29 and colonic fibroblast CCD-18Co cells were evaluated. Lentil BBI was able to inhibit the growth of such cells at concentrations higher than 19 μM, in a concentration-dependent manner; by contrast, the CCD18-Co cells were unaffected. These data broaden our knowledge of the beneficial biological activities of naturally-occurring BBI proteins and address the need for systematic evaluation of natural variants in order to design novel strategies in preventive medicine.     

Subspace Clustering for Situation Assessment in Aquatic Drones: A Sensitivity Analysis for State-Model Improvement

Abstract

In this paper, we propose the use of subspace clustering to detect the states of dynamical systems from sequences of observations. In particular, we generate sparse and interpretable models that relate the states of aquatic drones involved in autonomous water monitoring to the properties (e.g., statistical distribution) of data collected by drone sensors. The subspace clustering algorithm used is called SubCMedians. A quantitative experimental analysis is performed to investigate the connections between i) learning parameters and performance, ii) noise in the data and performance. The clustering obtained with this analysis outperforms those generated by previous approaches.     

A voltage tunable CMOS differential active resistor and its application

We propose a novel CMOS differential voltage-controlled equivalent active resistor based on a modified common-source cross-coupled pair. The equivalent resistance exhibited by the circuit can be tuned to be either positive or negative through the tail current, which is controlled by a bias voltage. The complete cell comprises four transistors, two resistors in addition to the bias voltage, and tail current source. Application to the design of oscillators is demonstrated by theoretical analysis, circuit simulations, and verified experimentally through measurements on prototypes implemented using discrete transistors.