Thermo-solvatochromism of merocyanine polarity probes - What are the consequences of increasing probe lipophilicity through annelation?

The question raised in the title has been answered by comparing the solvatochromism of two series of polarity probes, the lipophilicities of which were increased either by increasing the length of an alkyl group (R) attached to a fixed pyridine-based structure or through annelation (i.e., by fusing benzene rings onto a central pyridine-based structure). The following novel solvatochromic probes were synthesized: 2,6-dibromo-4-[(E)-2-(1-methylquinolinium-4-yl)ethenyl]-phenolate (MeQMBr(2)) and 2,6-dibromo-4-[(E)-2-(1-methyl-acridinium-4- yl) ethenyl)]phenolate (MeAMBr(2) The solvatochromic behavior of these probes, along with that of 2,6dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl]phenol-ate(MePMBr(2)) was analyzed in terms of increasing probe lipophilicity, through annelation. Values of the empirical solvent polarity scale [E(T)(MePMBr(2))] in kcalmol(-1) correlated linearly with ET(30), the corresponding values for the extensively employed probe 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (RB). On the other hand, the nonlinear correlations of ET(MeQMBr(2)) or ET(MeAMBr(2)) with E(T)(30) are described by second-order polynomials. Possible reasons for this behavior include: i) self-aggregation of the probe, ii) photoinduced cis/trans isomerization of the dye, and iii) probe structure- and solvent-dependent contributions of the quinonoid and zwitterionic limiting formulas to the ground and excited states of the probe. We show that mechanisms (i) and (ii) are not operative under the experimental conditions employed; experimental evidence (NMR) and theoretical calculations are presented to support the conjecture that the length of the central ethenylic bond in the dye increases in the order MeAMBr(2) > MeQMBr(2) > MePMBr(2), That is, the contribution of the zwitterionic limiting formula predominates for the latter probe, as is also the case for RB, this being the reason for the observed linear correlation between the ET(MePMBr2) and the ET(30) scales. The effect of increasing probe lipophilicity on solvatochromic behavior therefore depends on the strategy employed. Increasing the length of R affects solvatochromism much less than annelation, because the former structural change hardly perturbs the energy of the intramolecular charge-transfer transition responsible for solvatochromism. The thermo-solvatochromic behavior (effect of temperature on solvatochromism) of the three probes was studied in mixtures of water with propanol and/or with DMSO. The solvation model used explicitly considers the presence of three ""species"" in the system: bulk solution and probe solvation shell [namely, water (W), organic solvent (Solv)], and solvent-water hydrogen-bonded aggregate (Solv-W). For aqueous propanol, the probe is efficiently solvated by Solv-W; the strong interaction of DMSO with W drastically decreases the efficiency of Solv-W in solvating the probe, relative to its precursor solvents. Temperature increases resulted in desolvation of the probes, due to the concomitant reduction in the structured characters of the components of the binary mixtures.

A New Indirect Electroanalytical Method to Monitor the Contamination of Natural Waters with 4-Nitrophenol Using Multiwall Carbon Nanotubes

The electrochemical detection of the hazardous pollutant 4-nitrophenol (4-NP) at low potentials, in order to avoid matrix interferences, is an important research challenge. This study describes the development, electrochemical characterization and utilization of a multiwall carbon nanotube (MWCNT) film electrode for the quantitative determination of 4-NP in natural water. Electrochemical impedence spectroscopy measurements showed that the modified surface exhibits a decrease of ca. 13 times in the charge transfer resistance when compared with a bare glassy carbon (GC) surface. Voltammetric experiments showed the possibility to oxidize a hydroxylamine layer (produced by the electrochemical reduction of 4-NP on the GC/MWNCT surface) in a potential region which is approximately 700 mV less positive than that needed to oxidize 4-NP, thus minimizing the interference of matrix components. The limit of detection for 4-NP obtained using square-wave voltammetry (0.12 mu mol L(-1)) was lower than the value advised by EPA. A natural water sample from a dam located in Sao Carlos (Brazil) was spiked with 4-NP and analyzed by the standard addition method using thee GC/MWCNT electrode, without any further purification step. the recovery procedure yielded a value of 96.5% for such sample, thus confirming the suitability of the developed method to determine 4-NP in natural water samples. The electrochemical determination was compared with that obtained by HPLC with UV-vis detection.

Biotransformation of alpha-Bromoacetophenones by the Marine Fungus Aspergillus sydowii

The biotransformation reactions of alpha-bromoacetophenone (1), p-bromo-alpha-bromoacetophenone (2), and p-nitro-alpha-bromoacetophenone (3) by whole cells of the marine fungus Aspergillus sydowii Ce19 have been investigated. Fungal cells that had been grown in artificial sea water medium containing a high concentration of chloride ions (1.20 M) catalysed the biotransformation of 1 to 2-bromo-1-phenylethanol 4 (56%), together with the alpha-chlorohydrin 7 (9%), 1-phenylethan-1,2-diol 9 (26%), acetophenone 10 (4%) and phenylethanol 11 (5%) identified by GC-MS analysis. In addition, it was observed that the enzymatic reaction was accompanied by the spontaneous debromination of 1 to yield alpha-chloroacetophenone 5 (9%) and alpha-hydroxyacetophenone 6 (18%) identified by GC-FID analysis. When 2 and 3 were employed as substrates, various biotransformation products were detected but the formation of halohydrins was not observed. It is concluded that marine fungus A. sydowii Ce19 presents potential for the biotransformations of bromoacetophenone derivatives.

Bioreduction of alpha-chloroacetophenone by whole cells of marine fungi

The asymmetric reduction of 2-chloro-1-phenylethanone (1) by seven strains of marine fungi was evaluated and afforded (S)-(-)-2-chloro-1-phenylethanol with, in the best case, an enantiomeric excess of 50% and an isolated yield of 60%. The ability of marine fungi to catalyse the reduction was directly dependent on growth in artificial sea water-based medium containing a high concentration of Cl(-) (1.2 M). When fungi were grown in the absence of artificial sea water, no reduction of 1 by whole cells was observed. The biocatalytic reduction of 1 was more efficient at neutral rather than acidic pH values and in the absence of glucose as co-substrate.

Simulation of Photovoltaic Panel Production as Complement to Ground Source Heat Pump System

This master thesis presents a new technological combination of two environmentally friendly sources of energy in order to provide DHW, and space heating. Solar energy is used for space heating, and DHW production using PV modules which supply direct current directly to electrical heating elements inside a water storage tank. On the other hand a GSHP system as another source of renewable energy provides heat in the water storage tank of the system in order to provide DHW and space heating. These two sources of renewable energy have been combined in this case-study in order to obtain a more efficient system, which will reduce the amount of electricity consumed by the GSHP system.The key aim of this study is to make simulations, and calculations of the amount ofelectrical energy that can be expected to be produced by a certain amount of PV modules that are already assembled on a house in Vantaa, southern Finland. This energy is then intended to be used as a complement to produce hot water in the heating system of the house beside the original GSHP system. Thus the amount of electrical energy purchased from the grid should be reduced and the compressor in the GSHP would need fewer starts which would reduce the heating cost of the GSHP system for space heating and providing hot water.The produced energy by the PV arrays in three different circuits will be charged directly to three electrical heating elements in the water storage tank of the existing system to satisfy the demand of the heating elements. The excess energy can be used to heat the water in the water storage tank to some extent which leads to a reduction of electricity consumption by the different components of the GSHP system.To increase the efficiency of the existing hybrid system, optimization of different PV configurations have been accomplished, and the results are compared. Optimization of the arrays in southern and western walls shows a DC power increase of 298 kWh/year compared with the existing PV configurations. Comparing the results from the optimization of the arrays on the western roof if the intention is to feed AC power to the components of the GSHP system shows a yearly AC power production of 1,646 kWh.This is with the consideration of no overproduction by the PV modules during the summer months. This means the optimized PV systems will be able to cover a larger part of summer demand compared with the existing system.

Use of Photovoltaic on an E-bike? : A Feasibility Study

In recent years the number of bicycles with e-motors has been increased steadily. Within the pedelec – bikes where an e-motor supports the pedaling – a special group of transportation bikes has developed. These bikes have storage boxes in addition to the basic parts of a bike. Due to the space available on top of those boxes it is possible to install a PV system to generate electricity which could be used to recharge the battery of the pedelec. Such a system would lead to grid independent charging of the battery and to the possibility of an increased range of motor support. The feasibility of such a PV system is investigated for a three wheeled pedelec delivered by the company BABBOE NORDIC.The measured data of the electricity generation of this mobile system is compared to the possible electricity generation of a stationary system.To measure the consumption of the pedelec different tracks are covered, and the energy which is necessary to recharge the bike battery is measured using an energy logger. This recharge energy is used as an indirect measure of the electricity consumption. A PV prototype system is installed on the bike. It is a simple PV stand alone system consisting of PV panel, charge controller with MPP tracker and a solar battery. This system has the task to generate as much electricity as possible. The produced PV current and voltage aremeasured and documented using a data logger. Afterwards the average PV power is calculated. To compare the produced electricity of the on-bike system to that of a stationary system, the irradiance on the latter is measured simultaneously. Due to partial shadings on the on-bike PV panel, which are caused by the driver and some other bike parts, the average power output during riding the bike is very low. It is too low to support the motor directly. In case of a similar installation as the PV prototype system and the intention always to park the bike on a sunny spot an on-bike system could generate electricity to at least partly recharge a bike battery during one day. The stationary PV system using the same PV panel could have produced between 1.25 and 8.1 times as much as the on-bike PV system. Even though the investigation is done for a very specific case it can be concluded that anon-bike PV system, using similar components as in the investigation, is not feasible to recharge the battery of a pedelec in an appropriate manner. The biggest barrier is that partial shadings on the PV panel, which can be hardly avoided during operation and parking, result in a significant reduction of generated electricity. Also the installation of the on-bike PV system would lead to increased weight of the whole bike and the need for space which is reducing the storage capacity. To use solar energy for recharging a bike battery an indirect way is giving better results. In this case a stationary PV stand alone system is used which is located in a sunny spot without shadings and adjusted to use the maximum available solar energy. The battery of the bike is charged using the corresponding charger and an inverter which provides AC power using the captured solar energy.

Solar Collectors for Historic Homes : Linking consumption to perceptions of space

Reduction of household energy consumption is one of the top issues in contemporary discussions on sustainable consumption. This chapter concerns one way through which consumption of purchased energy for house heating can be reduced; by having a solar thermal system added to one's house. However, the fact that one of the components - the solar collector - usually is situated on the roof or the facade of a building, is a recurrent impediment to such installations. In certain contexts, these attributes may melt into the building, while in others, they may be perceived as problematic. The latter may particularly be the case when the appearance of the building is of major imiportance, as with houses deemed worthy of preservation for coming generations. This chapter draws upon a study carried out in Visby Town, a walled Hanseatic town and a World Heritage site on the island of Gotland, Sweden.