Thermodynamic Stabillity of Hydrogen-Bonded Systems in Polar and Nonpolar Environments

The thermodynamic properties of a selected set of benchmark hydrogen-bonded systems (acetic acid dimer and the complexes of acetic acid with acetamide and methanol) was studied with the goal of obtaining detailed information on solvent effects on the hydrogen-bonded interactions using water, chloroform, and n-heptane as representatives for a wide range in the dielectric constant. Solvent effects were investigated using both explicit and implicit solvation models. For the explicit description of the solvent, molecular dynamics and Monte Carlo simulations in the isothermal isobaric (NpT) ensemble combined with the free energy perturbation technique were performed to determine solvation free energies. Within the implicit solvation approach, the polarizable continuum model and the conductor-like screening model were applied. Combination of gas phase results with the results obtained from the different solvation models through an appropriate thermodynamic cycle allows estimation of complexation free energies, enthalpies, and the respective entropic contributions in solution. Owing to the strong solvation effects of water the cyclic acetic acid dimer is not stable in aqueous solution. In less polar solvents the double hydrogen bond structure of the acetic acid dimer remains stable. This finding is in agreement with previous theoretical and experimental results. A similar trend as for the acetic acid dimer is also observed for the acetamide complex. The methanol complex was found to be thermodynamically unstable in gas phase as well as in any of the three solvents. (C) 2010 Wiley Periodicals, Inc. J Comput Chem 31: 2046-2055, 2010

Solvent Effects in Chemical Processes. Water-Assisted Proton Transfer Reaction of Pterin in Aqueous Environment

Pterins are members of a family of heterocyclic compounds present in a wide variety of biological systems and may exist in two forms, corresponding to an acid and a basic tautomer. In this work, the proton transfer reaction between these tautomeric forms was investigated in the gas phase and in aqueous solution. In gas phase, the intramolecular mechanism was carried out for die isolated pterin by quantum mechanical second-order Moller-Plesset Perturbation theory (MP2/aug-cc-pVDZ) calculations and it indicates that the acid form is more stable than the basic form by -1.4 kcal/mol with a barrier of 34.2 kcal/mol with respect to the basic form. In aqueous solution, the role of the water molecules in the proton transfer reaction was analyzed in two separated parts, the direct participation of one water molecule in the reaction path, called water-assisted mechanism, and the complementary participation of the aqueous solvation. The water-assisted mechanism was carried out for one pterin-water cluster by quantum mechanical calculations and it indicates that the acid form is still more stable by -3.3 kcal/mol with a drastic reduction of 70% of the barrier, The bulk solution effect on the intramolecular and water-assisted mechanisms was included by free energy perturbation implemented on Monte Carlo simulations. The bulk water effect is found to be substantial and decisive when the reaction path involves the water-assisted mechanism. In this case, the free energy barrier is only 6.7 kcal/mol and the calculated relative Gibbs free energy for the two tautomers is -11.2 kcal/mol. This value is used to calculate the pK(a) value of 8.2 +/- 0.6 that is in excellent agreement with the experimental result of 7.9.

Effect of Different Solvent Ratios (Water/Ethylene Glycol) on the Growth Process of CaMoO(4) Crystals and Their Optical Properties

In this paper, calcium molybdate (CaMoO(4)) crystals (meso- and nanoscale) were synthesized by the coprecipitation method using different solvent volume ratios (water/ethylene glycol). Subsequently, the obtained suspensions were processed in microwave-assisted hydrothermal/solvothermal systems at 140 degrees C for 1 h. These meso- and nanocrystals processed were characterized by X-ray diffraction (X R I)), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR). ultraviolet visible (UV-vis) absorption spectroscopies, held-emission gun scanning electron microscopy (FEG-SEM). transmission electron microscopy (TEM). and photoluminescence (PL) measurements. X RI) patterns and FT-Raman spectra showed that these meso- and nanocrystals have a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 827 cm(-1), which is associated with the Mo-O anti-symmetric stretching vibrations into the [MoO(4)] clusters. FEG-SEM micrographs indicated that the ethylene glycol concentration in the aqueous solution plays an important role in the morphological evolution of CaMoO(4) crystals. High-resolution TEM micrographs demonstrated that the mesocrystals consist of several aggregated nanoparticles with electron diffraction patterns of monocrystal. In addition, the differences observed in the selected area electron diffraction patterns of CaMoO(4) crystals proved the coexistence of both nano- and mesostructures, First-principles quantum mechanical calculations based on the density functional theory at the B3LYP level were employed in order to understand the band structure find density of states For the CaMoO(4). UV-vis absorption measurements evidenced a variation in optical band gap values (from 3.42 to 3.72 cV) for the distinct morphologies. The blue and green PI. emissions observed in these crystals were ascribed to the intermediary energy levels arising from the distortions on the [MoO(4)] clusters clue to intrinsic defects in the lattice of anisotropic/isotropic crystals.

Disruption of Saccharomyces cerevisiae by Plantaricin 149 and investigation of its mechanism of action with biomembrane model systems

The action of a synthetic antimicrobial peptide analog of Plantaricin 149 (Pln149a) against Saccharomyces cerevisiae and its interaction with biomembrane model systems were investigated. Pln149a was shown to inhibit S. cerevisiae growth by more than 80% in YPD medium, causing morphological changes in the yeast wall and remaining active and resistant to the yeast proteases even after 24 h of incubation. Different membrane model systems and carbohydrates were employed to better describe the Pln149a interaction with cellular components using circular dichroism and fluorescence spectroscopies, adsorption kinetics and surface elasticity in Langmuir monolayers. These assays showed that Pln149a does not interact with either mono/polysaccharides or zwitterionic LUVs, but is strongly adsorbed to and incorporated into negatively charged surfaces, causing a conformational change in its secondary structure from random-coil to helix upon adsorption. From the concurrent analysis of Pln149a adsorption kinetics and dilatational surface elasticity data, we determined that 2.5 mu M is the critical concentration at which Pln149a will disrupt a negative DPPG monolayer. Furthermore, Pln149a exhibited a carpet-like mechanism of action, in which the peptide initially binds to the membrane, covering its surface and acquiring a helical structure that remains associated to the negatively charged phospholipids. After this electrostatic interaction, another peptide region causes a strain in the membrane, promoting its disruption. (C) 2009 Elsevier B.V. All rights reserved.

Langmuir Films of Petroleum at the Air-Water Interface

Understanding the behavior of petroleum films at the air/water interface is crucial for dealing with oil sticks and reducing the damages to the environment, which has normally been attempted with studies of Langmuir films made of fractions of petroleum. However, the properties of films from whole petroleum samples may differ considerably from those of individual fractions, Using surface pressure and surface potential measurements and Brewster angle and fluorescence microscopy, we show that petroleum forms it nonhomogeneous Langmuir film at the air-water interface. The surface pressure isotherms for petroleum Langmuir films exhibit gas (G), liquid-expanded (LE), and liquid-condensed phases, with almost no hysteresis in the compression-decompression cycles. Domains formed upon compression from the G to the LE phase were accompanied by an increase in fluorescence intensity with excitation at 400-440 nm owing to an increase in the surface density of the chromophores in the petroleum film. The surface pressure and the fluorescence microscopy data pointed to self-assembling domains into a pseudophase in thermo-dynamic equilibrium with other less emitting petroleum components. This hypothesis was supported by Brewster angle microscopy images, whereby the appearance of water domains even at high surface pressures confirms the tendency of petroleum to stabilize emulsion systems. The results presented here suggest that, for understanding the interaction with water, it may be more appropriate to use the whole petroleum samples rather than its fractions.

La(2-x)Ce(x)Cu(1-y)Zn(y)O(4) perovskites for high temperature water-gas shift reaction

The performance of La(2-x)Ce(x)Cu(1-y)Zn(y)O(4) perovskites as catalysts for the high temperature water-gas shift reaction (H T-W G S R) was investigated. The catalysts were characterized by EDS, XRD, BET surface area, TPR, and XANES. The results showed that all the perovskites exhibited the La(2)CuO(4) orthorhombic structure, so the Pechini method is suitable for the preparation of pure perovskite. However, the La(1.90)Ce(0.10)CuO(4) perovskite alone, when calcined at 350/700 degrees C, also showed a (La(0.935)Ce(0.065))(2)CuO(4) perovskite with tetragonal structure, which produced a surface area higher than the other perovskites. The perovskites that exhibited the best catalytic performance were those calcined at 350/700 degrees C and, among these, La(1.90)Ce(0.10)CuO(4) was outstanding, probably because of the high surface area associated with the presence of the (La(0.935)Ce(0.065))(2)CuO(4) perovskite with tetragonal structure and orthorhombic La(2)CuO(4) phase.

Load Adapted Solar Thermal Combisystems - Optical Analysis and Systems Optimization

In a northern European climate a typical solar combisystem for a single family house normally saves between 10 and 30 % of the auxiliary energy needed for space heating and domestic water heating. It is considered uneconomical to dimension systems for higher energy savings. Overheating problems may also occur. One way of avoiding these problems is to use a collector that is designed so that it has a low optical efficiency in summer, when the solar elevation is high and the load is small, and a high optical efficiency in early spring and late fall when the solar elevation is low and the load is large.The study investigates the possibilities to design the system and, in particular, the collector optics, in order to match the system performance with the yearly variations of the heating load and the solar irradiation. It seems possible to design practically viable load adapted collectors, and to use them for whole roofs ( 40 m2) without causing more overheating stress on the system than with a standard 10 m2 system. The load adapted collectors collect roughly as much energy per unit area as flat plate collectors, but they may be produced at a lower cost due to lower material costs. There is an additional potential for a cost reduction since it is possible to design the load adapted collector for low stagnation temperatures making it possible to use less expensive materials. One and the same collector design is suitable for a wide range of system sizes and roof inclinations. The report contains descriptions of optimized collector designs, properties of realistic collectors, and results of calculations of system output, stagnation performance and cost performance. Appropriate computer tools for optical analysis, optimization of collectors in systems and a very fast simulation model have been developed.

Report on IEA Task-14 activities on solar collector systems conference in Rome, 25-29 Jan. 1993

The memebers of IEA (International Energy Agency) Task 14 (Advaced Active Solar Systems) met in Rome during January 1993. The latest developments in several countries were presented and discussed during this meeting. This report describes briefly the recent work carried out on small scale systems in the Domestic Hot Water (DHW) working group of Task 14, as reported by the representatives from Canada, Denmark, Germany, Holland and Switzerland. Klaus Lorenz, SERC, attended the meeting as observer and presented our work on small-tube heat exchangers. Several participants expressed their interest. A summary of his presentation is included in this report.

Combined solar and pellet heating systems for single-family houses : How to achieve decreased electricity usage, increased system efficiency and increased solar gains

In Sweden, there are about 0.5 million single-family houses that are heated by electricity alone, and rising electricity costs force the conversion to other heating sources such as heat pumps and wood pellet heating systems. Pellet heating systems for single-family houses are currently a strongly growing market. Future lack of wood fuels is possible even in Sweden, and combining wood pellet heating with solar heating will help to save the bio-fuel resources. The objectives of this thesis are to investigate how the electrically heated single-family houses can be converted to pellet and solar heating systems, and how the annual efficiency and solar gains can be increased in such systems. The possible reduction of CO-emissions by combining pellet heating with solar heating has also been investigated. Systems with pellet stoves (both with and without a water jacket), pellet boilers and solar heating have been simulated. Different system concepts have been compared in order to investigate the most promising solutions. Modifications in system design and control strategies have been carried out in order to increase the system efficiency and the solar gains. Possibilities for increasing the solar gains have been limited to investigation of DHW-units for hot water production and the use of hot water for heating of dishwashers and washing machines via a heat exchanger instead of electricity (heat-fed appliances). Computer models of pellet stoves, boilers, DHW-units and heat-fed appliances have been developed and the parameters for the models have been identified from measurements on real components. The conformity between the models and the measurements has been checked. The systems with wood pellet stoves have been simulated in three different multi-zone buildings, simulated in detail with heat distribution through door openings between the zones. For the other simulations, either a single-zone house model or a load file has been used. Simulations were carried out for Stockholm, Sweden, but for the simulations with heat-fed machines also for Miami, USA. The foremost result of this thesis is the increased understanding of the dynamic operation of combined pellet and solar heating systems for single-family houses. The results show that electricity savings and annual system efficiency is strongly affected by the system design and the control strategy. Large reductions in pellet consumption are possible by combining pellet boilers with solar heating (a reduction larger than the solar gains if the system is properly designed). In addition, large reductions in carbon monoxide emissions are possible. To achieve these reductions it is required that the hot water production and the connection of the radiator circuit is moved to a well insulated, solar heated buffer store so that the boiler can be turned off during the periods when the solar collectors cover the heating demand. The amount of electricity replaced using systems with pellet stoves is very dependant on the house plan, the system design, if internal doors are open or closed and the comfort requirements. Proper system design and control strategies are crucial to obtain high electricity savings and high comfort with pellet stove systems. The investigated technologies for increasing the solar gains (DHW-units and heat-fed appliances) significantly increase the solar gains, but for the heat-fed appliances the market introduction is difficult due to the limited financial savings and the need for a new heat distribution system. The applications closest to market introduction could be for communal laundries and for use in sunny climates where the dominating part of the heat can be covered by solar heating. The DHW-unit is economical but competes with the internal finned-tube heat exchanger which is the totally dominating technology for hot water preparation in solar combisystems for single-family houses.

Dynamic whole system testing of combined renewable heating systems : the current state of the art

Objective: For the evaluation of the energetic performance of combined renewable heating systems that supply space heat and domestic hot water for single family houses, dynamic behaviour, component interactions, and control of the system play a crucial role and should be included in test methods. Methods: New dynamic whole system test methods were developed based on “hardware in the loop” concepts. Three similar approaches are described and their differences are discussed. The methods were applied for testing solar thermal systems in combination with fossil fuel boilers (heating oil and natural gas), biomass boilers, and/or heat pumps. Results: All three methods were able to show the performance of combined heating systems under transient operating conditions. The methods often detected unexpected behaviour of the tested system that cannot be detected based on steady state performance tests that are usually applied to single components. Conclusion: Further work will be needed to harmonize the different test methods in order to reach comparable results between the different laboratories. Practice implications: A harmonized approach for whole system tests may lead to new test standards and improve the accuracy of performance prediction as well as reduce the need for field tests.

System Integration of PV/T Collectors in Solar Cooling Systems

The demand for cooling and air-conditioning of building is increasingly ever growing. This increase is mostly due to population and economic growth in developing countries, and also desire for a higher quality of thermal comfort. Increase in the use of conventional cooling systems results in larger carbon footprint and more greenhouse gases considering their higher electricity consumption, and it occasionally creates peaks in electricity demand from power supply grid. Solar energy as a renewable energy source is an alternative to drive the cooling machines since the cooling load is generally high when solar radiation is high. This thesis examines the performance of PV/T solar collector manufactured by Solarus company in a solar cooling system for an office building in Dubai, New Delhi, Los Angeles and Cape Town. The study is carried out by analyzing climate data and the requirements for thermal comfort in office buildings. Cooling systems strongly depend on weather conditions and local climate. Cooling load of buildings depend on many parameters such as ambient temperature, indoor comfort temperature, solar gain to the building and internal gains including; number of occupant and electrical devices. The simulations were carried out by selecting a suitable thermally driven chiller and modeling it with PV/T solar collector in Polysun software. Fractional primary energy saving and solar fraction were introduced as key figures of the project to evaluate the performance of cooling system. Several parametric studies and simulations were determined according to PV/T aperture area and hot water storage tank volume. The fractional primary energy saving analysis revealed that thermally driven chillers, particularly adsorption chillers are not suitable to be utilizing in small size of solar cooling systems in hot and tropic climates such as Dubai and New Delhi. Adsorption chillers require more thermal energy to meet the cooling load in hot and dry climates. The adsorption chillers operate in their full capacity and in higher coefficient of performance when they run in a moderate climate since they can properly reject the exhaust heat. The simulation results also indicated that PV/T solar collector have higher efficiency in warmer climates, however it requires a larger size of PV/T collectors to supply the thermally driven chillers for providing cooling in hot climates. Therefore using an electrical chiller as backup gives much better results in terms of primary energy savings, since PV/T electrical production also can be used for backup electrical chiller in a net metering mechanism.

Testing of combined heating systems for small houses: Improved procedures for whole system test methods : Deliverable 2.3

Dynamic system test methods for heating systems were developed and applied by the institutes SERC and SP from Sweden, INES from France and SPF from Switzerland already before the MacSheep project started. These test methods followed the same principle: a complete heating system – including heat generators, storage, control etc., is installed on the test rig; the test rig software and hardware simulates and emulates the heat load for space heating and domestic hot water of a single family house, while the unit under test has to act autonomously to cover the heat demand during a representative test cycle. Within the work package 2 of the MacSheep project these similar – but different – test methods were harmonized and improved. The work undertaken includes:  • Harmonization of the physical boundaries of the unit under test. • Harmonization of the boundary conditions of climate and load. • Definition of an approach to reach identical space heat load in combination with an autonomous control of the space heat distribution by the unit under test. • Derivation and validation of new six day and a twelve day test profiles for direct extrapolation of test results.   The new harmonized test method combines the advantages of the different methods that existed before the MacSheep project. The new method is a benchmark test, which means that the load for space heating and domestic hot water preparation will be identical for all tested systems, and that the result is representative for the performance of the system over a whole year. Thus, no modelling and simulation of the tested system is needed in order to obtain the benchmark results for a yearly cycle. The method is thus also applicable to products for which simulation models are not available yet. Some of the advantages of the new whole system test method and performance rating compared to the testing and energy rating of single components are:  • Interaction between the different components of a heating system, e.g. storage, solar collector circuit, heat pump, control, etc. are included and evaluated in this test. • Dynamic effects are included and influence the result just as they influence the annual performance in the field. • Heat losses are influencing the results in a more realistic way, since they are evaluated under "real installed" and representative part-load conditions rather than under single component steady state conditions.   The described method is also suited for the development process of new systems, where it replaces time-consuming and costly field testing with the advantage of a higher accuracy of the measured data (compared to the typically used measurement equipment in field tests) and identical, thus comparable boundary conditions. Thus, the method can be used for system optimization in the test bench under realistic operative conditions, i.e. under relevant operating environment in the lab.   This report describes the physical boundaries of the tested systems, as well as the test procedures and the requirements for both the unit under test and the test facility. The new six day and twelve day test profiles are also described as are the validation results.

Human Health Impacts of Contaminants Found in Local Drinking Water Supply

Many contaminants are currently unregulated by the government and do not have a set limit, known as the Maximum Contaminant Level, which is dictated by cost and the best available treatment technology. The Maximum Contaminant Level Goal, on the other hand, is based solely upon health considerations and is non-enforceable. In addition to being naturally occurring, contaminants may enter drinking water supplies through industrial sources, agricultural practices, urban pollution, sprawl, and water treatment byproducts. Exposure to these contaminants is not limited to ingestion and can also occur through dermal absorption and inhalation in the shower. Health risks for the general public include skin damage, increased risk of cancer, circulatory problems, and multiple toxicities. At low levels, these contaminants generally are not harmful in our drinking water. However, children, pregnant women, and people with compromised immune systems are more vulnerable to the health risks associated with these contaminants. Vulnerable peoples should take additional precautions with drinking water. This research project was conducted in order to learn more about our local drinking water and to characterize our exposure to contaminants. We hope to increase public awareness of water quality issues by educating the local residents about their drinking water in order to promote public health and minimize exposure to some of the contaminants contained within public water supplies.

On Real-Time Monitoring And Control For Efficient Management Of Drinking Water Networks: Barcelona Case Study

Drinking water utilities in urban areas are focused on finding smart solutions facing new challenges in their real-time operation because of limited water resources, intensive energy requirements, a growing population, a costly and ageing infrastructure, increasingly stringent regulations, and increased attention towards the environmental impact of water use. Such challenges force water managers to monitor and control not only water supply and distribution, but also consumer demand. This paper presents and discusses novel methodologies and procedures towards an integrated water resource management system based on advanced ICT technologies of automation and telecommunications for largely improving the efficiency of drinking water networks (DWN) in terms of water use, energy consumption, water loss minimization, and water quality guarantees. In particular, the paper addresses the first results of the European project EFFINET (FP7-ICT2011-8-318556) devoted to the monitoring and control of the DWN in Barcelona (Spain). Results are split in two levels according to different management objectives: (i) the monitoring level is concerned with all the aspects involved in the observation of the current state of a system and the detection/diagnosis of abnormal situations. It is achieved through sensors and communications technology, together with mathematical models; (ii) the control level is concerned with computing the best suitable and admissible control strategies for network actuators as to optimize a given set of operational goals related to the performance of the overall system. This level covers the network control (optimal management of water and energy) and the demand management (smart metering, efficient supply). The consideration of the Barcelona DWN as the case study will allow to prove the general applicability of the proposed integrated ICT solutions and their effectiveness in the management of DWN, with considerable savings of electricity costs and reduced water loss while ensuring the high European standards of water quality to citizens.

From Smart Meters To Smart Decisions: Web-Based Support For The Water Efficient Household

Smart water metering technologies for residential buildings offer, in principle, great opportunities for sustainable urban water management. However, much of this potential is as yet unrealized. Despite that several ICT solutions have already been deployed aiming at optimum operations on the water utilities side (e.g. real time control for water networks, dynamic pump scheduling etc.), little work has been done to date on the consumer side. This paper presents a web-based platform targeting primarily the household end user. The platform enables consumers to monitor, on a real-time basis, the water demand of their household, providing feedback not only on the total water consumption and relevant costs but also on the efficiency (or otherwise) of specific indoor and outdoor uses. Targeting the reduction of consumption, the provided feedback is combined with notifications about possible leakages\bursts, and customised suggestions to improve the efficiency of existing household uses. It also enables various comparisons, with past consumption or even with that of similar households, aiming to motivate further the householder to become an active player in the water efficiency challenge. The issue of enhancing the platform’s functionality with energy timeseries is also discussed in view of recent advances in smart metering and the concept of “smart cities”. The paper presents a prototype of this web-based application and critically discusses first testing results and insights. It also presents the way in which the platform communicates with central databases, at the water utility level. It is suggested that such developments are closing the gap between technology availability and usefulness to end users and could help both the uptake of smart metering and awareness raising leading, potentially, to significant reductions of urban water consumption. The work has received funding from the European Union FP7 Programme through the iWIDGET Project, under grant agreement no318272.