Evaluation of isopentane, R-245fa and their mixtures as working fluids for organic Rankine cycles

Low grade thermal energy from sources such as solar, geothermal and industrial waste heat in the temperature range of 380-425 K can be converted to electrical energy with reasonable efficiency using isopentane and R-245fa. While the former is flammable and the latter has considerable global warming potential, their mixture in 0.7/0.3 mole fraction is shown to obviate these disadvantages and yet retain dominant merits of each fluid. A realistic thermodynamic analysis is carried out wherein the possible sources of irreversibilities such as isentropic efficiencies of the expander and the pump and entropy generation in the regenerator, boiler and condenser are accounted for. The performance of the system in the chosen range of heat source temperatures is evaluated. A technique of identifying the required source temperature for a given output of the plant and the maximum operating temperature of the working fluid is developed. This is based on the pinch point occurrence in the boiler and entropy generation in the boiling and superheating regions of the boiler. It is shown that cycle efficiencies of 10-13% can be obtained in the range investigated at an optimal expansion ratio of 7-10. (C) 2012 Elsevier Ltd. All rights reserved.

Discrimination of alpha-Amino Acids Using Green Tea Flavonoid (-)-Epigallocatechin Gallate as a Chiral Solvating Agent

We report a special, hitherto-unexplored property of (-)-epigallocatechin gallate (EGCG) as a chiral solvating agent for enantiodiscrimination of alpha-amino acids in the polar solvent DMSO. This phenomenon has been investigated by H-1 NMR spectroscopy. The mechanism of the interaction property of EGCG with alpha-amino acids has been understood as arising out of hydrogen-bonded noncovalent interactions, where the -OH groups of two phenyl rings of EGCG play dominant roles. The conversion of the enantiomeric mixture into diastereomers yielded well-resolved peaks for D and L amino acids permitting the precise measurement of enantiomeric composition. Often one encounters complex situations when the spectra are severely overlapped or partially resolved hampering the testing of enantiopurity and the precise measurement of enantiomeric excess (ee). Though higher concentration of EGCG yielded better discrimination, the use of lower concentration being economical, we have exploited an appropriate 2D NMR experiment in overcoming such problems. Thus, in the present study we have successfully demonstrated the utility of the bioflavonoid (-)-EGCG, a natural product as a chiral solvating agent for the discrimination of large number of alpha-amino acids in a polar solvent DMSO. Another significant advantage of this new chiral sensing agent is that it is a natural product and does not require tedious multistep synthesis unlike many other chiral auxiliaries.

Polyvinylbutyral based hybrid organic/inorganic films as a moisture barrier material

Flexible and thermally stable, freestanding hybrid organic/inorganic based polymer-composite films have been fabricated using a simple solution casting method. Polyvinylbutyral and amine functionalized mesoporous silica were used to synthesize the composite. An additional polyol-''tripentaerythritol''-component was also used to increase the -OH group content in the composite matrix. The moisture permeability of the composites was investigated by following a calcium degradation test protocol. This showed a reduction in the moisture permeability with the increase in functionalized silica loadings in the matrix. A reduction in permeability was observed for the composites as compared to the neat polymer film. The thermal and mechanical properties of these composites were also investigated by various techniques like thermogravimetric analysis, differential scanning calorimetry, tensile experiments, and dynamic mechanical analysis. It was observed that these properties detonate with the increase in the functionalized silica content and hence an optimized loading is required in order to retain critical properties. This deterioration is due to the aggregation of the fillers in the matrix. Furthermore, the films were used to encapsulate P3HT (poly 3 hexyl thiophene) based organic Schottky structured diodes, and the diode characteristics under accelerated aging conditions were studied. The weathered diodes, encapsulated with composite film showed an improvement in the lifetime as compared to neat polymer film. The initial investigation of these films suggests that they can be used as a moisture barrier layer for organic electronics encapsulation application.

Evaluation of carbon dioxide blends with isopentane and propane as working fluids for organic Rankine cycles

The main theme of this paper is to study the flammability suppression of hydrocarbons by blending with carbon dioxide, and to evaluate these mixtures as possible working fluids in organic Rankine cycle for medium temperature concentrated solar power applications. The analysis takes into account inevitable irreversibilities in the turbine, the pump, and heat exchangers. While the isopentane + CO2 mixture suffers from high irreversibility mainly in the regenerator owing to a large temperature glide, the propane + CO2 mixture performs more or less the same as pure propane albeit with high cycle pressures. In general, large temperature glides at condensing pressures extend the heat recovery into the two-phase dome, which is an advantage. However, at the same time, the shift of the pinch point towards the warm end of the regenerator is found to be a major cause of irreversibility. In fact, as the number of carbon atoms in alkanes decreases, their blend with CO2 moves the pinch point to the colder end of the regenerator. This results in lower entropy generation in the regenerator and improved cycle efficiency of propane + CO2 mixtures. With this mixture, real cycle efficiencies of 15-18% are achievable at a moderate source temperature of 573 K. Applicability for a wide range of source temperatures is found to be an added advantage of this mixture.

Mechanical properties of a metal-organic framework containing hydrogen-bonded bifluoride linkers

We report the mechanical properties of a framework structure, Cu2F(HF)(HF2)(pyz)(4)](SbF6)(2)](n) (pyz = pyrazine), in which Cu(pyz)(2)](2+) layers are pillared by HF2- anions containing the exceptionally strong F-H center dot center dot center dot F hydrogen bonds. Nanoindentation studies on single-crystals clearly demonstrate that such bonds are extremely robust and mechanically comparable with coordination bonds in this system.

Diaminotriazine substituted diphenyl ether: reversible structural transformation and solvent dependent solid state fluorescence

The effect of molecular shape and position of hydrogen bonding functionality in the solid state structural self-assembly was investigated using diaminotriazine substituted diphenyl ether based positional isomers (1-5). The molecular shape was modulated by changing diaminotriazine position that produced channel supramolecular structures in 1, 3 and 5. There exists a direct correlation between the molecular shape and three dimensional structures; more linear molecules resulted in close-packing whereas molecules with a labyrinthine topology formed a channel structure. Supramolecular aspects pertaining to the influence of solvent of crystallization in structure formation and reversible structural transformation in solid state were also explored. 1-5 exhibited tunable solid state fluorescence (lambda(max) = 437-496 nm) depending on the diaminotriazine substitutional position and 3 showed solvent-dependent solid state fluorescence. The present study describes the generation of a supramolecular channel structure with functional properties such as tunable fluorescence by varying the position of hydrogen bond functionality and solvent of crystallization.

Ionomer based blend as water vapor barrier material for organic device encapsulation

Blends of poly (ethylene-co-methacrylic acid) (PEMA) and poly (vinyl alcohol-co-ethylene) (EVOH) were studied for encapsulating Schottky structured organic devices. A calcium degradation test was used to determine water vapor transmission rates and to determine the moisture barrier performance of neat and blend films. Moisture barrier analysis for the neat and blend compositions was discussed concerning the interactions in the blend, diffusivity of water molecules through the unit cell systems, and the occupiable free volumes available in the unit cells using molecular dynamics simulations. The experimental results of water vapor permeation were correlated with diffusion behavior predicted from molecular dynamics simulations results. The effectiveness of the blend as a suitable barrier material in increasing the lifetime of an encapsulated Schottky structured organic device was determined.

C12-Helix development in ()n sequences - spectroscopic characterization of Boc-Aib-4(R)Val]-OMe oligomers

The solution conformations of the -hybrid oligopeptides Boc-Aib-4(R)Val]n-OMe (n = 1-8) in organic solvents have been probed by NMR, IR, and CD spectroscopic methods. In the solid state, this peptide series favors C12-helical conformations, which are backbone-expanded analogues of 310 helices in -peptide sequences. NMR studies of the six- (n = 3) and 16-residue (n = 8) peptides reveal that only two NH protons attached the N-terminus residues Aib(1) and 4(R)Val(2) are solvent-exposed. Sequential NiH-Ni+1H NOEs characteristic of local helical conformations are also observed at the residues. IR studies establish that chain extension leads to a large enhancement in the intensities of the hydrogen-bonded NH stretching bands (3343-3280 cm-1), which suggest elongation of intramolecularly hydrogen-bonded structures. The development of C12-helical structures upon lengthening of the sequence is supported by the NMR and IR observations. The CD spectra of the ()n peptides reveal a negative maximum at ca. 206 nm and a positive maximum at ca. 192 nm, spectral feature that are distinct from those of 310 helices in -peptides.

Ellagic acid - a novel organic electrode material for high capacity lithium ion batteries

Ellagic acid, a naturally occurring polyphenol, extracted from pomegranate husk, is found to be a very good organic electrode material for rechargeable lithium batteries with high reversible capacities of similar to 450 and 200 mA h g(-1) at C/10 and C/2.5 discharge rates, respectively; ex situ NMR studies reveal possible lithiation-delithiation modes at different stages of the charge-discharge process.

Flexible poly(vinyl alcohol-co-ethylene)/modified MMT moisture barrier composite for encapsulating organic devices

Flexible, nano-composite moisture barrier films of poly(vinyl alcohol-co-ethylene) with surface modified montmorillonite fabricated by solution casting were used to encapsulate organic devices. The composite films were characterized by FTIR, UV-visible spectroscopy and SEM imaging. Thermal and mechanical properties of the composite films were studied by DSC and UTM. Calcium degradation test was used to determine the transmission rate of water vapour through the composite films, which showed a gradual reduction from similar to 0.1 g m(-2) day(-1) to 0.0001 g m(-2) day(-1) with increasing modified montmorillonite loading in the neat copolymer. The increase in moisture barrier performance is attributed to the decreased water vapour diffusivity due to matrix-filler interactions in the composite. The accelerated aging test was carried out for non-encapsulated and encapsulated devices to evaluate the efficiency of the encapsulants. The encapsulated devices exhibited longer lifetimes indicating the efficacy of the encapsulant.

Crystal engineering: from molecule to crystal

How do molecules aggregate in solution, and how do these aggregates consolidate themselves in crystals? What is the relationship between the structure of a molecule and the structure of the crystal it forms? Why do some molecules adopt more than one crystal structure? Why do some crystal structures contain solvent? How does one design a crystal structure with a specified topology of molecules, or a specified coordination of molecules and/or ions, or with a specified property? What are the relationships between crystal structures and properties for molecular crystals? These are some of the questions that are being addressed today by the crystal engineering community, a group that draws from the larger communities of organic, inorganic, and physical chemists, crystallographers, and solid state scientists. This Perspective provides a brief historical introduction to crystal engineering itself and an assessment of the importance and utility of the supramolecular synthon, which is one of the most important concepts in the practical use and implementation of crystal design. It also provides a look to the future from the viewpoint of the author, and indicates some directions in which this field might be moving.

Solvent-templated supramolecular isomerism in 2D coordination polymer constructed by (Ni2CoII)-Co-II nodes and dicyanamido spacers: drastic change in magnetic behaviours

Two heterometallic coordination polymers (CPs) have been prepared using (NiL)-L-II](2)Co-II (where H2L = N,N'-bis(salicylidene)-1,3-propanediamine) as nodes and dicyanamido spacers by varying the solvent for synthesis. Structural characterizations revealed that methanol assisted the formation of a two-dimensional (4,4) connected rhombic grid network of (NiL)(2)Co(NCNCN)2](infinity) (1a) whereas relatively less polar acetonitrile afforded a different superstructure {(NiL)(2)Co(NCNCN)(2)]center dot CH3CN}(infinity) (1b) with a two-dimensional (4,4) connected square grid network. The presence of acetonitrile molecules in the structure of 1b seems to change the spatial orientation of the terminal metalloligands NiL] from pseudo-eclipsed in 1a to staggered-like in 1b around the central Co(II). These structural changes in the nodes together with the conformationally flexible dicyanamido spacers, which are cis coordinated to the Co(II) in both trinuclear units, led to the differences in the final 2D network. Variable-temperature magnetic susceptibility measurements revealed that this supramolecular isomerism led to a drastic transition from spin-frustrated antiferromagnetism for 1a to a dominant ferromagnetic behaviour for 1b. The geometrical differences in Ni2Co coordination clusters (CCs) which are scalene triangular in 1a but nearly linear in 1b, are held responsible for the changes of the magnetic properties. The DFT calculations of exchange interactions between metal centres provide a clear evidence of the role played by the fundamental geometrical factors on the nature and magnitude of the magnetic coupling in these pseudo-polymorphic CPs.

Biogeochemical facsimile of the organic matter quality and trophic status of a micro-tidal tropical estuary

Seasonal studies were carried out from 21 stations, comprising of three zones, of Cochin Estuary, to assess the organic matter quality and trophic status. The hydographical parameters showed significant seasonal variations and nutrients and chlorophylls were generally higher during the monsoon season. However, chemical contamination along with the seasonal limitations of light and nitrogen imposed restrictions on the primary production and as a result, mesotrophic conditions generally prevailed in the water column. The nutrient stoichometries and delta C-13 values of surficial sediments indicated significant allochthonous contribution of organic matter. Irrespective of the higher content of total organic matter, the labile organic matter was very low. Dominance of carbohydrates over lipids and proteins indicated the lower nutritive aspect of the organic matter, and their aged and refractory nature. This, along with higher amount of phytodetritus and the low algal contribution to the biopolymeric carbon corroborated the dominance of allochthonous organic matter and the heterotrophic nature. The spatial and seasonal variations of labile organic components could effectively substantiate the observed shift in the productivity pattern. An alternative ratio, lipids to tannins and lignins, was proposed to ascertain the relative contribution of allochthonous organic matter in the estuary. This study confirmed the efficiency of an integrated biogeochemical approach to establish zones with distinct benthic trophic status associated with different degrees of natural and anthropogenic input. Nevertheless, our results also suggest that the biochemical composition alone could lead to erroneous conclusions in the case of regions that receive enormous amounts of anthropogenic inputs.

Information content of molecular graph and prediction of gas phase thermal entropy of organic compounds

Entropy is a fundamental thermodynamic property that has attracted a wide attention across domains, including chemistry. Inference of entropy of chemical compounds using various approaches has been a widely studied topic. However, many aspects of entropy in chemical compounds remain unexplained. In the present work, we propose two new information-theoretical molecular descriptors for the prediction of gas phase thermal entropy of organic compounds. The descriptors reflect the bulk and size of the compounds as well as the gross topological symmetry in their structures, all of which are believed to determine entropy. A high correlation () between the entropy values and our information-theoretical indices have been found and the predicted entropy values, obtained from the corresponding statistically significant regression model, have been found to be within acceptable approximation. We provide additional mathematical result in the form of a theorem and proof that might further help in assessing changes in gas phase thermal entropy values with the changes in molecular structures. The proposed information-theoretical molecular descriptors, regression model and the mathematical result are expected to augment predictions of gas phase thermal entropy for a large number of chemical compounds.

Diketopyrrolopyrrole-Based Conjugated Polymers and Small Molecules for Organic Ambipolar Transistors and Solar Cells

The present highlight discusses major work in the synthesis of low bandgap diketopyrrolopyrrole (DPP)-based polymers with donor-acceptor-donor (D-A-D) approach and their application in organic electronics. It examines the past and recent significant advances which have led to development of low bandgap DPP-based materials with phenyl and thiophene as donors. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4241-4260