CHLORAL HYDRATE AS A WATER CARRIER FOR THE EFFICIENT DEPROTECTION OF ACETALS, DITHIOACETALS, AND TETRAHYDROPYRANYL ETHERS IN ORGANIC SOLVENTS

The efficient deprotection of several acetals, dithioacetals, and tetrahydropyranyl (THP) ethers under ambient conditions, using chloral hydrate in hexane, is described. Excellent yields were realized for a wide range of both aliphatic and aromatic substrates. The method is characterized by mild conditions (room temperatures or below), simple workup, and the ready availability of chloral hydrate. High chemoselectivity was also observed in the deprotection, acetonides, esters, and amides being unaffected under the reaction conditions. Products were generally purified chromatographically and identified spectrally. These results constitute a novel addition to current methodology involving a widely employed deprotection tactic in organic synthesis. It seems likely that the mechanism of the reaction involves adsorption of the substrate on the surface of the sparingly soluble chloral hydrate.

Conducting polymer-carbon black nanocomposite sensor for volatile organic compounds and correlating sensor response by molecular dynamics

Volatile organic compounds (VOCs) are present in our every day used products such as plastics, cosmetics, air fresheners, paint, etc. The determination of amount of VOC present in atmosphere can be carried out via various sensors. In this work a nanocomposite of a novel thiophene based conducting polymer and carbon black is used as a volatile organic compound sensor. The fabricated 2 lead chemiresistor sensor was tested for vapours of toluene, acetone, cylcohexane, and carbon tetrachloride. The sensor responds to all the vapours, however, exhibit maximum response to toluene vapours. The sensor was evaluated for various concentrations of toluene. The lower limit of detection of the sensor is 15 +/- 10 ppm. The study of the effect of humidity on senor response to toluene showed that the response decreases at higher humidity conditions. The surface morphology of the nanocomposite was characterized by scanning electron microscopy. Diffuse reflectance spectroscopy was used to investigate the absorption of vapours by the nanocomposite film. Contact angle measurements were used to present the effect of water vapour on the toluene response of nanocomposite film. Solubility parameter of the conducting polymer is predicted by molecular dynamics. The sensing behaviour of the conducting polymer is correlated with solubility parameter of the polymer. Dispersion interaction of conducting polymer with toluene is believed to be the reason for the selective response towards toluene. (C) 2014 Elsevier B.V. All rights reserved.

Design Aspects of Luminescent Organic Crystals

With the progress of modern material science and successful commercialisations of organic-electronics, the field of organic luminescent materials has gained much attention in recent years. For a long time, the concepts and knowledge of photoluminescence (i.e. fluorescence and phosphorescence) were restricted to the solution phase as the exceptions of fluorescence quenching in condensed state were yet to be discovered. However, in the last few decades, researchers around the globe have come up with a number of promising strategies and concepts to systematically design solid-state emissive organic materials. In particular, the manipulations of ordered solid state structures and intermolecular strong and weak interactions provide a basis for understanding structure-property relationship and serve as an important tool for the design of newer, better and more efficient luminescent materials. In this short review, recent developments in this field will be presented.

Organic white-light emitting materials

Full-color emissive organic materials have attracted significant attention in recent years as key components in display and lighting devices based on OLEDs. An ideal white-light emitter demands simultaneous emission of red, green and blue with nearly similar distribution of intensities covering the entire region of visible spectra. However, the design of such white-light emitters is not straightforward. Mixing several emitters is seldom successful owing to the negative effects of intermolecular interactions and energy transfer processes. Nonetheless, these fundamental questions have been addressed in recent times by several research groups of vastly different expertise leading to a considerable progress in the field of organic white-light emitters. The designs cover a large area of the chemistry ranging from frustrated energy transfer to simple protonation or from designed self-assembly to simple mixing of materials. In this review, the concepts and rational approaches underlying the design of white-light emissive organic materials are described. (C) 2014 Elsevier Ltd. All rights reserved.

Fabrication of large-area PbSe films at the organic-aqueous interface and their near-infrared photoresponse

An organic-aqueous interfacial reaction at room temperature has been employed to synthesize large-area self-assembled films consisting of PbSe single crystallites. The use of the films for the low-cost fabrication of IR-photodetectors has been explored. (111)-oriented single crystallites of PbSe self-assemble to form robust large-area films. The near-infrared photoresponse of the film measured at room temperature showed large responsivity and gain owing to trap-associated mechanisms. Low-cost, mild reaction conditions and tunability of the nature of deposits make the present strategy useful for synthesizing large-area films of functional materials for possible opto-electronic applications.

A modeling study of the processes of surface salinity seasonal cycle in the Bay of Bengal

In response to the Indian Monsoon freshwater forcing, the Bay of Bengal exhibits a very strong seasonal cycle in sea surface salinity (SSS), especially near the mouths of the Ganges-Brahmaputra and along the east coast of India. In this paper, we use an eddy-permitting (similar to 25 km resolution) regional ocean general circulation model simulation to quantify the processes responsible for this SSS seasonal cycle. Despite the absence of relaxation toward observations, the model reproduces the main features of the observed SSS seasonal cycle, with freshest water in the northeastern Bay, particularly during and after the monsoon. The model also displays an intense and shallow freshening signal in a narrow (similar to 100 km wide) strip that hugs the east coast of India, from September to January, in good agreement with high-resolution measurements along two ships of opportunity lines. The mixed layer salt budget confirms that the strong freshening in the northern Bay during the monsoon results from the Ganges-Brahmaputra river discharge and from precipitation over the ocean. From September onward, the East India Coastal Current transports this freshwater southward along the east coast of India, reaching the southern tip of India in November. The surface freshening results in an enhanced vertical salinity gradient that increases salinity of the surface layer by vertical processes. Our results reveal that the erosion of the freshwater tongue along the east coast of India is not driven by northward horizontal advection, but by vertical processes that eventually overcome the freshening by southward advection and restore SSS to its premonsoon values. The salinity-stratified barrier layer hence only acts as a ``barrier'' for vertical heat fluxes, but is associated with intense vertical salt fluxes in the Bay of Bengal.

Organic solar cell by using vertically aligned nanostructured ZnO nanorods

A low temperature solution approach was employed to grow zinc oxide (ZnO) nanorods with various aspect ratios. Various sizes (diameter-10-25nm) of the nanorods were grown by changing the concentrations of the growth solution. The length (50nm-500nm) of nanorods was controlled using growth times. These one-dimensional (1D) nanostructures with direct paths for a charge transport with high surface area for light harvesting, are promising candidates for organic photovoltaics (OPV). The structural and optical properties of the prepared ZnO nanorods have been studied using SEM, XRD and UV-Vis absorption spectroscopy. Using as-grown ZnO inverted OPV was fabricated. ZnO nanorods were subjected to various doses of UV-ozone irradiation which led to improvement in transmission and hence enhanced device performance.

POLAR NETWORK INDEX AS A MAGNETIC PROXY FOR THE SOLAR CYCLE STUDIES

The Sun has a polar magnetic field which oscillates with the 11 yr sunspot cycle. This polar magnetic field is an important component of the dynamo process which operates in the solar convection zone and produces the sunspot cycle. We have direct systematic measurements of the Sun's polar magnetic field only from about the mid-1970s. There are, however, indirect proxies which give us information about this field at earlier times. The Ca-K spectroheliograms taken at the Kodaikanal Solar Observatory during 1904-2007 have now been digitized with 4k x 4k CCD and have higher resolution (similar to 0.86 arcsec) than the other available historical data sets. From these Ca-K spectroheliograms, we have developed a completely new proxy (polar network index, hereafter PNI) for the Sun's polar magnetic field. We calculate PNI from the digitized images using an automated algorithm and calibrate our measured PNI against the polar field as measured by the Wilcox Solar Observatory for the period 1976-1990. This calibration allows us to estimate the polar fields for the earlier period up to 1904. The dynamo calculations performed with this proxy as input data reproduce reasonably well the Sun's magnetic behavior for the past century.

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.

Organic passivation layer on flexible Surlyn substrate for encapsulating organic photovoltaics

Barrier materials are required for encapsulating organic devices. A simple methodology based on organic passivation layer on a flexible substrate has been developed in this work. Stearyl stearate ( SS) was directly coated over the flexible Surlyn film. The barrier films with SS passivation layer exhibited much lower water vapor transmission rates compared to the neat Surlyn films. Moreover, the effect of the process of deposition of organic passivation layer on the resultant water vapor properties of the barrier films was evaluated. The accelerated lifetime studies conducted on encapsulated organic photovoltaics showed that the passivation layer improved the device performance by several fold compared to the non-passivated barrier films. (C) 2014 AIP Publishing LLC.

Pyridylenevinylene based Cu2+-specific, injectable metallo(hydro) gel: thixotropy and nanoscale metal-organic particles

A Cu2+-selective metallo(hydro) gelation of a p-pyridyl ended oligophenylenevinylene system is reported over its respective meta- and ortho-regioisomers. The metallogel formed via the self-assembly of the nanoscale-metal-organic particles is injectable and also shows multi-stimuli responsiveness, including thixotropy.

Multicomponent Assembly of Fluorescent-Tag Functionalized Ligands in Metal-Organic Frameworks for Sensing Explosives

Detection of trace amounts of explosive materials is significantly important for security concerns and pollution control. Four multicomponent metal organic frameworks (MOFs-12, 13, 23, and 123) have been synthesized by employing ligands embedded with fluorescent tags. The multicomponent assembly of the ligands was utilized to acquire a diverse electronic behavior of the MOFs and the fluorescent tags were strategically chosen to enhance the electron density in the MOFs. The phase purity of the MOFs was established by PXRD, NMR spectroscopy, and finally by singlecrystal XRD. Single-crystal structures of the MOFs-12 and 13 showed the formation of three-dimensional porous networks with the aromatic tags projecting inwardly into the pores. These electron-rich MOFs were utilized for detection of ex- plosive nitroaromatic compounds (NACs) through fluorescence quenching with high selectivity and sensitivity. The rate of fluorescence quenching for all the MOFs follows the order of electron deficiency of the NACs. We also showed the detection of picric acid (PA) by luminescent MOFs is not always reliable and can be misleading. This attracts our attention to explore these MOFs for sensing picryl chloride (PC), which is as explosive as picric acid and used widely to prepare more stable explosives like 2,4,6-trinitroaniline from PA. Moreover, the recyclability and sensitivity studies indicated that these MOFs can be reused several times with parts per billion (ppb) levels of sensitivity towards PC and 2,4,6-trinitrotoluene (TNT).

New low band gap 2-(4-(trifluoromethyl)phenyl)-1H-benzod]imidazole and benzo1,2-c; 4,5-c `]bis1,2,5]thiadiazole based conjugated polymers for organic photovoltaics

Two new low band gap D-A structured conjugated polymers, PBDTTBI and PBDTBBT, based on 2-(4-(trifluoromethyl)phenyl)-1H-benzod]imidazole and benzo1,2-c; 4,5-c']bis1,2,5]thiadiazole acceptor units with benzo1,2-b; 3,4-b']dithiophene as a donor unit have been designed and synthesized via a Stille coupling reaction. The incorporation of the benzo1,2-c; 4,5-c']bis1,2,5]thiadiazole unit into PBDTBBT has significantly altered the optical and electrochemical properties of the polymer. The optical band gap estimated from the onset absorption edge is similar to 1.88 eV and similar to 1.1 eV, respectively for PBDTTBI and PBDTBBT. It is observed that PBDTBBT exhibited a deeper HOMO energy level (similar to 4.06 eV) with strong intramolecular charge transfer interactions. Bulk heterojunction solar cells fabricated with a configuration of ITO/PEDOT: PSS/PBDTBBT: PC71BM/Al exhibited a best power conversion efficiency of 0.67%, with a short circuit current density of 4.9 mA cm(-2), an open-circuit voltage of 0.54 V and a fill factor of 25%.

Self-Assembled, Aligned ZnO Nanorod Buffer Layers for High-Current-Density, Inverted Organic Photovoltaics

Two different soft-chemical, self-assembly-based solution approaches are employed to grow zinc oxide (ZnO) nanorods with controlled texture. The methods used involve seeding and growth on a substrate. Nanorods with various aspect ratios (1-5) and diameters (15-65 nm) are grown. Obtaining highly oriented rods is determined by the way the substrate is mounted within the chemical bath. Furthermore, a preheat and centrifugation step is essential for the optimization of the growth solution. In the best samples, we obtain ZnO nanorods that are almost entirely oriented in the (002) direction; this is desirable since electron mobility of ZnO is highest along this crystallographic axis. When used as the buffer layer of inverted organic photovoltaics (I-OPVs), these one-dimensional (1D) nanostructures offer: (a) direct paths for charge transport and (b) high interfacial area for electron collection. The morphological, structural, and optical properties of ZnO nanorods are studied using scanning electron microscopy, X-ray diffraction, and ultraviolet-visible light (UV-vis) absorption spectroscopy. Furthermore, the surface chemical features of ZnO films are studied using X-ray photoelectron spectroscopy and contact angle measurements. Using as-grown ZnO, inverted OPVs are fabricated and characterized. For improving device performance, the ZnO nanorods are subjected to UV-ozone irradiation. UV-ozone treated ZnO nanorods show: (i) improvement in optical transmission, (ii) increased wetting of active organic components, and (iii) increased concentration of Zn-O surface bonds. These observations correlate well with improved device performance. The devices fabricated using these optimized buffer layers have an efficiency of similar to 3.2% and a fill factor of 0.50; this is comparable to the best I-OPVs reported that use a P3HT-PCBM active layer.