Synthesis of inorganic solids using microwaves

Use of microwaves in the synthesis of materials is gaining importance. Microwave-assisted synthesis is generally much faster, cleaner, and more economical than the conventional methods. A variety of materials such as carbides, nitrides, complex oxides, silicides, zeolites, apatite, etc. have been synthesized using microwaves. Many of these are of industrial and technological importance. An understanding of the microwave interaction with materials has been based on concepts of dielectric heating and of the resonance absorption due to rotational excitation. This review presents a summary of recent reports of microwave synthesis of inorganic materials. Various observations regarding microwave interaction with materials are also briefly discussed.

Perfluoroalkyl bile esters: a new class of efficient gelators of organic and aqueous-organic media

A new class of fluorinated gelators derived from bile acids is reported. Perfluoroalkyl chains were attached to the bile acids through two different ester linkages and were synthesized following simple transformations. The gelation property of these derivatives is a function of the bile acid moiety, the spacer and the fluoroalkyl chain length. By varying these parameters, gels were obtained in aromatic hydrocarbons, DMSO and DMSO/DMF-H(2)O mixtures of different proportions. Several derivatives of deoxycholic and lithocholic acids were found to be efficient organogelators, while the reported bile-acid based organogelators are mostly derived from the cholic acid moiety. The efficient gelators among these compounds formed gels well below 1.0% (w/v) and hence they can be termed as supergelators. The mechanical properties of these gels could be modulated by changing either the bile acid moiety or by varying the length of the fluoroalkyl segment. The presence of CO(2)-philic perfluoroalkyl groups is also expected to enhance their solubility in supercritical CO(2) and hence these compounds are promising candidates for making aerogels.

Perfluoroalkyl bile esters: a new class of efficient gelators of organic and aqueous-organic media

A new class of fluorinated gelators derived from bile acids is reported. Perfluoroalkyl chains were attached to the bile acids through two different ester linkages and were synthesized following simple transformations. The gelation property of these derivatives is a function of the bile acid moiety, the spacer and the fluoroalkyl chain length. By varying these parameters, gels were obtained in aromatic hydrocarbons, DMSO and DMSO/DMF-H(2)O mixtures of different proportions. Several derivatives of deoxycholic and lithocholic acids were found to be efficient organogelators, while the reported bile-acid based organogelators are mostly derived from the cholic acid moiety. The efficient gelators among these compounds formed gels well below 1.0% (w/v) and hence they can be termed as supergelators. The mechanical properties of these gels could be modulated by changing either the bile acid moiety or by varying the length of the fluoroalkyl segment. The presence of CO(2)-philic perfluoroalkyl groups is also expected to enhance their solubility in supercritical CO(2) and hence these compounds are promising candidates for making aerogels.

Nanostructured barbed wire architecturing of organic conducting material blends by electrospinning

In this study, fibers of barbed wire structure were obtained by electrospinning blend of organic conducting crystalline material and polyethylene oxide. Thermal and structural characterization of the blend fibers has been carried out to study the fiber characteristics. An increase in crystallinity in the electrospun fibers was observed and was attributed to both electrospinning process as well as addition of organic conducting crystalline material. A mechanism for the formation of this barbed wire structure has also been proposed. (C) 2012 American Institute of Physics. [doi:10.1063/1.3673620]

First-Principles Study of the Effect of Organic Ligands on the Crystal Structure of CdS Nanoparticles

We show with the aid of first-principles electronic structure calculations that suitable choice of the capping ligands may be an important control parameter for crystal structure engineering of nanoparticles. Our calculations on CdS nanocrystals reveal that the binding energy of model trioctylphosphine molecules on the (001) facets of zincblende nanocrystals is larger compared to that on wurtzite facets. Similarly, the binding energy of model cis-oleic acid is found to be dominant for the (10 (1) over bar0) facets of wurtzite structure. As a consequence, trioctylphosphine as a capping agent stabilizes the zincblende structure while cis-oleic acid stabilizes the wurtzite phase by influencing the surface energy, which has a sizable contribution to the energetics of a nanocrystal. Our detailed analysis suggests that the binding of molecules on the nanocrystalline facets depends on the surface topology of the facets, the coordination of the surface atoms where the capping molecule is likely to attach, and the conformation of the capping molecule.

Degradation studies of organic acids in commercially packed fruit juices: A reverse phase high performance liquid chromatographic approach

Organic acids are important constituents of fruit juices. They render tartness, flavour and specific taste to fruit juices. Shelf life and stability of fruit juices are important factors, which determine their nutritional quality and freshness. In this view, the effect of storage on the concentration of organic acids in commercially packed fruit juices is studied by reverse phase high performance liquid chromatography (RP-HPLC). Ten packed fruit juices from two different brands are stored at 30 C for 24, 48 and 72 hours. A reverse phase high performance liquid chromatographic method is used to determine the concentration of oxalic, tartaric, malic, ascorbic and citric acid in the fruit juices during storage. The chromatographic analysis of organic acids is carried out using mobile phase 0.5% (w/v) ammonium dihydrogen orthophosphate buffer (pH 2.8) on C18 column with UV-Vis detector. The results show that the concentration of organic acids generally decreases in juices under study with the increase in storage time. All the fruit juices belonging to tropicana brand underwent less organic acid degradation in comparison to juices of real brand. Orange fruit juice is found to be least stable among the juices under study, after the span of 72 hours. Amongst all the organic acids under investigation minimum stability is shown by ascorbic acid followed by malic and citric acid.

Time-Temperature Scaling of Conductivity Spectra of Organic Plastic Crystalline Conductors

Organic plastic crystalline soft matter ion conductors are interesting alternatives to liquid electrolytes in electrochemical storage devices such as Lithium-ion batteries. The solvent dynamics plays a major role in determining the ion transport in plastic crystalline ion conductors. We present here an analysis of the frequency-dependent ionic conductivity of succinonitrile-based plastic crystalline ion conductors at varying salt composition (0.005 to 1 M) and temperature (-20 to 60 degrees C) using time-temperature superposition principle (TTSP). The main motivation of the work has been to establish comprehensive insight into the ion transport mechanism from a single method viz, impedance spectroscopy rather than employing cluster of different characterization methods probing various length and time scales. The TTSP remarkably aids in explicit identification of the extent of the roles of solvent dynamics and ion-ion interactions on the effective conductivity of the orientationally disordered plastic crystalline ion conductors.

Effect of Stress and Interface defects on Photo Luminescence of Si nano-crystals embedded in SiO2

Effect of stress and interface defects on photo luminescence property of a silicon nano-crystal (Si-nc) embedded in amorphous silicon dioxide (a-SiO2) are studied in this paper using a self-consistent quantum-continuum based modeling framework. Si-ncs or quantum dots show photoluminescence at room temperature. Whether its origin is due to Si-nc/a-SiO2 interface defects or quantum confinement of carriers in Si-nc is still an outstanding question. Earlier reports have shown that stresses greater than 12 GPa change the indirect energy band gap structure of bulk Si to a direct energy band gap structure. Such stresses are observed very often in nanostructures and these stresses influence the carrier confinement energy significantly. Hence, it is important to determine the effect of stress in addition to the structure of interface defects on photoluminescence property of Si-nc. In the present work, first a Si-nc embedded in a-SiO2 is constructed using molecular dynamics simulation framework considering the actual conditions they are grown so that the interface and residual stress in the structure evolves naturally during formation. We observe that the structure thus created has an interface of about 1 nm thick consisting of 41.95% of defective states mostly Sin+ (n = 0 to 3) coordination states. Further, both the Si-nc core and the embedding matrix are observed to be under a compressive strain. This residual strain field is applied in an effective mass k.p Hamiltonian formulation to determine the energy states of the carriers. The photo luminescence property computed based on the carrier confinement energy and interface energy states associated with defects will be analysed in details in the paper.

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.

Modelling of optical transport behavior of organic photovoltaic devices with nano-pillar transparent conducting electrodes

Optical transport behavior of organic photo-voltaic devices with nano-pillar transparent electrodes is investigated in this paper in order to understand possible enhancement of their charge-collection efficiency. Modeling and simulations of optical transport due to this architecture show an interesting regime of length-scale dependent optical characteristics. An electromagnetic wave propagation model is employed with simulation objectives toward understanding the mechanism of optical scattering and waveguide effects due to the nano-pillars and effective transmission through the active layer. Partial filling of gaps between the nano-pillars due to the nano-fabrication process is taken into consideration. Observations made in this paper will facilitate appropriate design rules for nano-pillar electrodes. (C) 2014 AIP Publishing LLC.

Strategy for Enhancing the Dielectric Constant of Organic Semiconductors Without Sacrificing Charge Carrier Mobility and Solubility

Current organic semiconductors for organic photovoltaics (OPV) have relative dielectric constants (relative permittivities, epsilon(r)) in the range of 2-4. As a consequence, Coulombically bound electron-hole pairs (excitons) are produced upon absorption of light, giving rise to limited power conversion efficiencies. We introduce a strategy to enhance epsilon(r) of well-known donors and acceptors without breaking conjugation, degrading charge carrier mobility or altering the transport gap. The ability of ethylene glycol (EG) repeating units to rapidly reorient their dipoles with the charge redistributions in the environment was proven via density functional theory (DFT) calculations. Fullerene derivatives functionalized with triethylene glycol side chains were studied for the enhancement of epsilon(r) together with poly(p-phenylene vinylene) and diketo-pyrrolopyrrole based polymers functionalized with similar side chains. The polymers showed a doubling of epsilon(r) with respect to their reference polymers in identical backbone. Fullerene derivatives presented enhancements up to 6 compared with phenyl-C-61-butyric acid methyl ester (PCBM) as the reference. Importantly, the applied modifications did not affect the mobility of electrons and holes and provided excellent solubility in common organic solvents.