Photophysical, electrochemical and solid state properties of diketopyrrolopyrrole based molecular materials: importance of the donor group

Diketopyrrolopyrrole (DPP) based molecular semiconductors have emerged as promising materials for high performance active layers in organic solar cells. It is imperative to comprehend the origin of such a property by investigating the fundamental structure property correlation. In this report we have investigated the role of the donor group in DPP based donor-acceptor- donor (D-A-D) structure to govern the solid state, photophysical and electrochemical properties. We have prepared three derivatives of DPP with varying strengths of the donor groups, such as phenyl (PDPP-Hex), thiophene (TDPP-Hex) and selenophene (SeDPP-Hex). The influence of the donor units on the solid state packing was studied by single crystal X-ray diffraction. The photophysical, electrochemical and density functional theory ( DFT) results were combined to elucidate the structural and electronic properties of three DPP derivatives. We found that these DPP derivatives crystallized in the monoclinic space group P21/c and show herringbone packing in the crystal lattice. The derivatives exhibit weak p-p stacking interactions as two neighboring molecules slip away from each other with varied torsional angles at the donor units. The high torsional angle of 32 degrees ( PDPP-Hex) between the phenyl and lactam ring results in weak intramolecular interactions between the donor and acceptor, while TDPP-Hex and SeDPP-Hex show lower torsional angles of 9 degrees and 12 degrees with a strong overlap between the donor and acceptor units. The photophysical properties reveal that PDPP-Hex exhibits a high Stokes shift of 0.32 eV and SeDPP- Hex shows a high molar absorption co-efficient of 33 600 L mol -1 1 cm -1 1 with a low band gap of similar to 2.2 eV. The electrochemical studies of SeDPP- Hex indicate the pronounced effect of selenium in stabilizing the LUMO energy levels and this further emphasizes the importance of chalcogens in developing new n-type organic semiconductors for optoelectronic devices.

Mechanical and thermal modeling of In-Cu composites for thermal interface materials applications

In-Cu composite solders have been proposed as an effective thermal interface material. Here, finite element analysis and theoretical treatment of their mechanical and thermal behavior is presented. It was determined that the stresses and the strains were concentrated in the narrow and wider In channels, respectively. Furthermore, it is suggested that an In-Cu composite with disk-shaped Cu inclusions may not only further improve the thermal conductivity but may also reduce the stiffness of In-Cu composites in shear.

The influence of mesoporous silica in low T-g cyclic olefin copolymer nanocomposite films: Mechanical and moisture barrier studies

In this study, mesoporous silica-cyclic olefin copolymer nanocomposite films were fabricated by solution casting. With an increase in silica loading, the stiffness of the matrix increased. The nanocomposite film shows increased strain to failure with moisture after aging by matrix plasticization. The storage modulus and loss factor for samples with silica content show better results compared with pristine polymer, as indicated by dynamic mechanical analysis. The interaction between filler-polymer chain exhibit hydrophobicity compared to the neat polymer. Water absorption studies at room temperature and near the T-g of the polymer (similar to 64 degrees C) were carried out. The nanocomposites up to 4 wt% filler reduces the water diffusion by forming hydrogen and chemical bonding. The result by calcium degradation test method for moisture permeability and Schottky structured organic device encapsulation under weathering condition confirms the effective reinforcement effect of silica particles in the matrix. (C) 2014 Elsevier Ltd. All rights reserved.

Polyanhydrides of Castor Oil-Sebacic Acid for Controlled Release Applications

A family of high molecular weight castor oil (CO)-based biodegradable polyanhydrides was synthesized by a catalyst-free melt-condensation reaction between prepolymers of CO and sebacic acid (SA). The structure of the polymers was characterized by H-1 NMR and Fourier transform infrared spectroscopy, which indicated the formation of the anhydride bond along the polymer backbone. Thermal analysis and X-ray diffraction confirmed the semicrystalline nature of the polymers. Incorporation of SA enhanced the crystallinity of the polymer. The hydrophobic nature of these polymers was revealed by contact angle goniometry. Water wettability decreased with increase in SA content. Compressive tests demonstrated a sharp increase in strength and decrease in ductility with increasing SA content. In vitro hydrolytic degradation studies indicated surface-eroding behavior. The degradation rate decreased with an increase of SA content in the polymers because of increased crystallinity. The release studies of both hydrophobic and hydrophilic dyes followed zero-order kinetics. In vitro cell studies to assess the cytotoxicity of the polymer confirmed minimal toxicity of the degradation products. Thus, a family of CO-SA polyanhydrides have been synthesized and characterized for controlled release applications where the physical, mechanical, and degradation kinetics can be modulated by varying the weight fraction of the prepolymers.

Morphology controlled synthesis of wurtzite ZnS nanostructures through simple hydrothermal method and observation of white light emission from ZnO obtained by annealing the synthesized ZnS nanostructures

A controllable synthesis of phase pure wurtzite (WZ) ZnS nanostructures has been reported in this work at a low temperature of similar to 220 degrees C using ethylenediamine as the soft template and by varying the molar concentration of zinc to sulphur precursors as well as by using different precursors. A significant reduction in the formation temperature required for the synthesis of phase pure WZ ZnS has been observed. A strong correlation has been observed between the morphology of the synthesized ZnS nanostructures and the precursors used during synthesis. It has been found from Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) image analyses that the morphology of the ZnS nanocrystals changes from a block-like to a belt-like structure having an average length of similar to 450 nm when the molar ratio of zinc to sulphur source is increased from 1 : 1 to 1 : 3. An oriented attachment (OA) growth mechanism has been used to explain the observed shape evolution of the synthesized nanostructures. The synthesized nanostructures have been characterized by the X-ray diffraction technique as well as by UV-Vis absorption and photoluminescence (PL) emission spectroscopy. The as-synthesized nanobelts exhibit defect related visible PL emission. On isochronal annealing of the nanobelts in air in the temperature range of 100-600 degrees C, it has been found that white light emission with a Commission Internationale de I'Eclairage 1931 (CIE) chromaticity coordinate of (0.30, 0.34), close to that of white light (0.33, 0.33), can be obtained from the ZnO nanostructures obtained at an annealing temperature of 600 degrees C. UV light driven degradation of methylene blue (MB) dye aqueous solution has also been demonstrated using as-synthesized nanobelts and similar to 98% dye degradation has been observed within only 40 min of light irradiation. The synthesized nanobelts with visible light emission and having dye degradation activity can be used effectively in future optoelectronic devices and in water purification for cleaning of dyes.

Enhanced viability of probiotic Saccharomyces boulardii encapsulated by layer-by-layer approach in pH responsive chitosan-dextran sulfate polyelectrolytes

Saccharomyces boulardii was encapsulated by layer-by-layer technique (LbL) using oppositely charged polyelectrolytes, chitosan and dextran sulfate to protect from degradation during its gastrointestinal transit. The protective effect of the coating was evaluated by checking viability after subjecting the coated cells to lyophilisation and simulated gastrointestinal conditions. During lyophilization, coated S. boulardii was found to have an enhanced viability of 7.74 +/- 2.00 log CFU/100 mg (5.62 x 10(6) +/- 2.12 CFU/100 mg) and 5.53 +/- 1.85 log CFU/100 mg (3.46 x 10(5) 1.73 CFU/100 mg) for uncoated cells. On sequential treatment with simulated gastric and intestinal juice, the coated cells had a viability of 4.59 +/- 1.52 log CFU/100 mg (3.8 x 104 +/- 1.52 CFU/100 mg) while only 1.90 +/- 0.80 log CFU/100 mg (0.79 x 102 +/- 0.81 CFU/100 mg) of uncoated cells survived. Confocal studies displayed the selective permeability of the coated cells which plays a significant role in maintaining the integrity and viability of the yeast cells. This clearly indicates that LbL is an efficient protective encapsulation technique and it could be potentially used for improving therapeutic applications of yeast. (C) 2014 Elsevier Ltd. All rights reserved.

Biodegradable Mg and Mg based alloys for biomedical implants

Mg and its alloys become natural biomaterials as the elemental Mg is found in the human body in abundance and their mechanical properties being akin to the natural bone as well as due to their inherent bioabsorbable/bioresorbable property. This paper discusses the development of new Mg alloys and their corrosion characteristics in detail. The latest advancements in coating of Mg alloys to control their degradation rate are also reviewed along with the future challenges that need to be addressed.

C. N. R. Rao and the Growth of Solid State and Materials Chemistry as a Central Domain of Research

In celebrating Professor C. N. R. Rao's 80th birthday, this article recalls his singular contributions to solid state and materials chemistry for about sixty years. In so doing, the article also traces the growth of the field as a central domain of research in chemical sciences from its early origins in Europe. Although Rao's major work lies in solid state and materials chemistry - a field which he started and nurtured in India while its importance was being recognized internationally - his contributions to other areas of chemistry (and physics), viz., molecular spectroscopy, phase transitions, fullerenes, graphene, nanomaterials and multiferroics are equally significant. Illustrative examples of his work devoted to rare earth and transition metal oxides, defects and nonstoichiometry, metal-insulator transitions, investigation of crystal and electronic structures of a variety of solids by means of electron microscopies and photoelectron spectroscopy, superconducting cuprates, magnetoresistive manganites, multiferroic metal oxides of various structures and, last but not the least, development of new strategies for chemical synthesis of a wide variety of solids including nanomaterials and framework solids in different dimensionalities, are highlighted. The article also captures his exemplary role as a science teacher, science educationist and institution builder in post-Independence India.

Raman spectroscopy explores molecular structural signatures of hidden materials in depth: Universal Multiple Angle Raman Spectroscopy

Non-invasive 3D imaging in materials and medical research involves methodologies such as X-ray imaging, MRI, fluorescence and optical coherence tomography, NIR absorption imaging, etc., providing global morphological/density/absorption changes of the hidden components. However, molecular information of such buried materials has been elusive. In this article we demonstrate observation of molecular structural information of materials hidden/buried in depth using Raman scattering. Typically, Raman spectroscopic observations are made at fixed collection angles, such as, 906, 1356, and 1806, except in spatially offset Raman scattering (SORS) (only back scattering based collection of photons) and transmission techniques. Such specific collection angles restrict the observations of Raman signals either from or near the surface of the materials. Universal Multiple Angle Raman Spectroscopy (UMARS) presented here employs the principle of (a) penetration depth of photons and then diffuse propagation through non-absorbing media by multiple scattering and (b) detection of signals from all the observable angles.

Detailed understanding of the excitation-intensity dependent photoluminescence of ZnO materials: Role of defects

The photoluminescence (PL) of ZnO is shown to be dependent on the excitation intensity (EI) of the laser, and the substantial shift observed in the band to band transition is attributed to the heating effect. In order to understand this phenomenon in detail, we investigate the EI dependent PL of various ZnO samples systematically from liquid nitrogen (LN) to room temperature by varying the laser power. Some of the samples exhibit substantial red shift in the band to band transition with increasing EI even in LN environment, negligible effect is observed for others. Hence, our results strongly suggest that the EI dependent PL is not a characteristic of all ZnO samples. This indicates that laser-induced heating effect is not the dominant factor that governs the shifts in the PL spectra. Rather, the defect level excitation accounts for such observation. (C) 2014 AIP Publishing LLC.

First-Principles Study of Structure, Vibrational, and Elastic Properties of Stoichiometric and Calcium-Deficient Hydroxyapatite

Hydroxyapatite (HAp), a primary constituent of human bone, is usually nonstoichiometric with varying Ca/P molar ratios, with the well-known fact that Ca deficiency can cause marked reductions in its mechanical properties. To gain insights into the mechanism of this degradation, we employ first-principles calculations based on density functional theory and determine the effects of Ca deficiency on structure, vibrational, and elastic properties of HAp. Our simulation results confirm a considerable reduction in the elastic constants of HAp due to Ca deficiency, which was experimentally reported earlier. Stress-induced transformation of the Ca-deficient defected structure into a metastable state upon the application of stress could be a reason for this. Local structural stability of HAp and Ca-deficient HAp structures is assessed with full phonon dispersion studies. Further, specific signatures in the computed vibrational spectra for Ca deficiency in HAp can be utilized in experimental characterization of different types of defected HAp.

Effect of silane functionalized alumina on poly(vinyl butyral) nanocomposite films: Thermal, mechanical, and moisture barrier studies

In this work, a hybrid-polymer nanocomposite film, based on polyvinyl butyral/amino-silane functionalized nano alumina, was fabricated by melt processing. The calcium degradation measurements suggest the functionalized nanocomposite films exhibit higher resistance towards moisture penetration as compared to the neat alumina loaded films. Thermal stability, mechanical strength, and contact angle studies of the composites were also conducted to evaluate the performance of the functionalized alumina loaded films. These nanocomposite films were encapsulated over Al/P3HT/ITO Schottky structured device. The changes observed in the current density of the devices to the applied voltage before and after accelerated aging conditions are presented. The nanocomposite with functionalized alumina films exhibits 50% change in current density, which is superior to that attained with neat and non-functionalized films. POLYM. COMPOS., 35:1426-1435, 2014. (c) 2013 Society of Plastics Engineers

Surface Degradation of Silicone Rubber Nanocomposites Due to DC Corona Discharge

Corona discharge is recognized as one of the mechanisms that can influence the surface hydrophobicity of Silicone Rubber (SR) because of the chemical changes that occur on its surface. In this study SR samples were exposed to positive and negative DC corona for 25 and 50 hours using a needle-plane electrode system. Hydrophobicity changes were monitored using a sessile drop contact angle measurement facility. The physical changes on the surface were studied using Scanning Electron Microscopy (SEM) and surface roughness measurements. The effect of positive dc corona was found to be different from that of negative dc corona. Significant surface degradation and loss of hydrophobicity was found in the case of negative dc corona exposed samples. Significant improvement in the above mentioned properties were obtained by adding small quantities of nSIL into the SR matrix.

Generalized scaling of misorientation angle distributions at meso-scale in deformed materials

Scaling behaviour has been observed at mesoscopic level irrespective of crystal structure, type of boundary and operative micro-mechanisms like slip and twinning. The presence of scaling at the meso-scale accompanied with that at the nano-scale clearly demonstrates the intrinsic spanning for different deformation processes and a true universal nature of scaling. The origin of a 1/2 power law in deformation of crystalline materials in terms of misorientation proportional to square root of strain is attributed to importance of interfaces in deformation processes. It is proposed that materials existing in three dimensional Euclidean spaces accommodate plastic deformation by one dimensional dislocations and their interaction with two dimensional interfaces at different length scales. This gives rise to a 1/2 power law scaling in materials. This intrinsic relationship can be incorporated in crystal plasticity models that aim to span different length and time scales to predict the deformation response of crystalline materials accurately.

New columnar liquid crystal materials based on luminescent 2-methoxy-3-cyanopyridines

A new series of donor-acceptor-donor (D-A-D) type luminescent mesogens carrying 2-methoxy-3-cyanopyridine as a central core linked with variable alkoxy chain lengths (m = 6 and 8) as terminal substituents was synthesized and characterized using spectral methods. The newly synthesized molecules were subjected to single-crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), differential scanning calorimetric (DSC), polarizing optical microscopy (POM), and fluorescence emission studies in order to ascertain their mesogenic and photophysical properties. The SCXRD data on 4a and 4b reveal that the presence of short intermolecular contacts, viz. C-H center dot center dot center dot N, C-H center dot center dot center dot O, C-H center dot center dot center dot pi, and pi center dot center dot center dot pi interactions, is responsible for their crystal packing. The measured torsion angle values indicate that molecules possess distorted non-planar structure. The DSC, POM, and PXRD studies confirm that all the molecules show thermotropic liquid crystalline behaviour and exhibit rectangular columnar phase. Further, their UV-visible and fluorescence spectral studies reveal that the target molecules are luminescent displaying a strong absorption band in the range of 335-340 nm and a blue fluorescence emission band in the range of 395-425 nm (both in solution and film state) with good fluorescence quantum yields (10-49 %).