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The structure of poly(vinyl alcohol) (PVA) hydrogels formed as a result of freeze/thaw treatments of aqueous solutions of the polymer (11 wt % PVA) in the freshly prepared state is analyzed through the combined use of small (SANS) and ultrasmall (USANS) angle neutron scattering techniques. The structure of these hydrogels may be described in terms of polymer rich regions, with dimensions of the order of 1−2 m, dispersed in a water rich phase, forming two bicontinuous phases. The PVA chains in the polymer rich phase form a network where the cross-linking points are mainly crystalline aggregates of PVA having average dimensions of ∼45 Å. The structural organization of freeze/thaw PVA hydrogel membranes does not change either after rehydration of dried gels or in the presence of a tensile force. Finally, addition of surfactant micelles inside the gel provides a formulation with both hydrophobic and hydrophilic regions, which demonstrates the potential of the system for drug delivery. Both SANS and EPR measurements show that sodium decylsulfate (C10OS) micelles do not significantly interact with the PVA gel. Variation of the gel structure by the number of freeze/thaw cycles should modulate the rate of release of an active constituent, for example, in a dermal patch. [ABSTRACT FROM AUTHOR]

Biocompatible bone implants composed of natural materials are highly desirable in orthopedic reconstruction procedures. In this study, novel and ecofriendly bionanocomposite hydrogels were synthesized using a blend of hydroxypropyl guar (HPG), poly vinyl alcohol (PVA), and nano-hydroxyapatite (n-HA) under freeze-thaw and mild reaction conditions. The hydrogel materials were characterized using various techniques. TGA studies indicate that both composites, HPG/PVA and HPG/PVA/n-HA, have higher thermal stability compared to HPG alone whereas HPG/PVA/n-HA shows higher stability compared to PVA alone. The HPG/PVA hydrogel shows porous morphology as revealed by the SEM, which is suitable for bone tissue regeneration. Additionally, the hydrogels were found to be transparent and flexible in nature. In vitro biomineralization study performed in simulated body fluid shows HPG/PVA/n-HA has an apatite like structure. The hydrogel materials were employed as extracellular matrices for biocompatibility studies. In vitro cell viability studies using mouse osteoblast MC3T3 cells were performed by MTT, Trypan blue exclusion, and ethidium bromide/acridine orange staining methods. The cell viability studies reveal that composite materials support cell growth and do not show any signs of cytotoxicity compared to pristine PVA. Osteoblastic activity was confirmed by an increased alkaline phosphatase enzyme activity in MC3T3 bone cells grown on composite hydrogel matrices. [ABSTRACT FROM AUTHOR]

ABSTRACT The synthesis and characterization of two low band gap copolymers ( P1 and P2) incorporating benzo[1,2- b:4,5- b']dithiophene unit substituted with octylsulfanylthienyl groups (OSBT) are here reported. These materials, designed to be employed in polymer solar cells (PSCs), were obtained from alternating OSBT and bithiophene ( P1) or thienothiophene ( P2) units. Their structural electrochemical and photophysical properties were investigated. They are thermally stable and soluble in organic solvents from which they easily form films. They also form π-stacks in solution, in film and display a moderate solvatochromism. These polymers were tested with [70]PCBM in bulk-heterojunction (BHJ) PSCs where they act as donor materials and [70]PCBM is the electron acceptor. The best device, obtained using a 1:3 weight ratio for the P1:[70]PCBM blend, shows a PCE around 1.5%. A broad response from 350 to 700 nm is also observed in the external quantum efficiency (EQE) curves, wider for P1 with respect to P2. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1603-1614 [ABSTRACT FROM AUTHOR]

A detailed study of reduction potentials, electroreduction mechanisms, and acid-base chemistry was carried out on two series of free-base porphyrins in nonaqueous media. The first series is represented by four β-pyrrole-substituted tetraphenylporphyrin (TPP) derivatives, two of which are planar and two of which are nonplanar in their nonprotonated form. The second comprises porphyrins with 0-4 meso-phenyl groups on the macrocycle. Equilibrium constants for the conversion of each neutral porphyrin to its diprotic [H4P]2+ form were determined and the electrochemistry was then elucidated as a function of: 1) type of nonaqueous solvent, 2) anion of supporting electrolyte, 3) porphyrin ring substituents, and 4) concentration of acid added to solution. Spectroelectrochemistry was used to characterize absorption spectra of each electroreduced species and, when combined with results of the above studies, significantly improves our ability to tune redox reactivity of these types of compounds. [ABSTRACT FROM AUTHOR]

In this work, we report the application of a sol-gel derived ZnO thin film as a buffer layer for high efficiency inverted polymer solar cells. ZnO films are widely used in such devices because they have a relatively high electron mobility, high transparency and environmental stability. The ZnO precursor was prepared by dissolving zinc acetate and ethanolamine in the 2-methoxyethanol. ZnO thin films were then deposited on indium tin oxide (ITO)/glass substrates by spin coating the above solution. Inverted polymer solar cells with the configuration ITO/ZnO/photoactive layer/MoO/Ag were realized in order to investigate the performance of ZnO thin film. The photoactive layer is a blend of poly[(4,8-bis-(2-ethylhexyloxy)-benzo[1,2-b;4,5-b′]dithiophene)-2,6-diyl-alt-(4-(2-ethylhexanoyl)-thieno[3,4-b]thiophene)-2,6-diyl] (PBDTTT-C) and [6,6]-phenyl C butyric acid methyl ester ([70]PCBM) (1:1.5 w/w). We made a comparative study of the photovoltaic behavior of devices with ZnO films deposited using different sol-gel recipes. In particular, we varied the zinc acetate/ethanolamine molar ratio to have ZnO films with different trace amounts of starting materials. In addition we also prepared ZnO films annealed at 200 °C for different times (from 5′ to 60′) in order to evaluate this effect on the trace amount removal. [ABSTRACT FROM AUTHOR]

Many research efforts are focused toward significant improvements of polymeric solar cells efficiency, energy harvesting range, time, and environmental stability. Particular attention is given to hybrid organic/inorganic composites constituted of polymer/lead chalcogenides (PbS and PbSe) nanocrystals (NCs) to extend the spectral sensitivity of cells to near-infrared wavelengths. In this work we report the synthesis and characterization of PbS nanocrystals with absorption edge at 984 nm. The nanocrystals have a cubic crystal structure and size of about 2 nm as found by X-ray diffraction analysis. They were combined with poly(3-hexylthiophene) (P3HT) polymer to obtain P3HT:PbS blends with different PbS loadings. A post-deposition ligand exchange on PbS NCs by 1,2-ethanedithiol (EDT) allowed a better interaction between polymer and nanocrystals as showed by fluorescence measurements. The P3HT:PbS blends were deposited and treated by a layer by layer spin coating process and used as active layer in solar cells having structure glass/ITO/PEDOT:PSS/blend/Al. The major result obtained for this hybrid system is an increase of PCE by about two orders of magnitude with respect to analogous reported cells where a post-deposition ligand exchange was performed. [ABSTRACT FROM AUTHOR]

Monolithic aerogels can be easily obtained by drying physical gels formed by linear uncross-linked polymers. Preparation methods, structure, and properties of these physically cross-linked polymeric aerogels are reviewed, with particular emphasis to those whose cross-linking knots are crystallites and, more in particular, crystallites exhibiting nanoporous-crystalline forms. The latter aerogels present beside disordered amorphous micropores (typical of all aerogels) also all identical nanopores of the crystalline phases. Their outstanding guest transport properties combined with low material cost, robustness, durability, and ease of handling and recycle make these aerogels suitable for applications in chemical separations, purification, and storage as well as in biomedicine. Scientific, technological, and industrial perspectives for monolithic nanoporous-crystalline polymeric aerogels are also discussed. [ABSTRACT FROM AUTHOR]

Substoichiometric molybdenum oxide (MoOx) has good potential as a hole-collecting layer in solar cells. In this paper, we report on the application of ultrathin evaporated MoOx as a hole collector at the back side of two distinct photovoltaic technologies: polymeric and silicon heterojunction (SHJ). In the case of polymer solar cells, we test MoOx as a hole transport layer in devices with inverted architecture. The higher transparency of the MoOx film, compared to the commonly used poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), allows an enhanced back reflected light into the photoactive layer, thus boosting the photogeneration, as found from the illuminated J-V and external quantum efficiency (EQE) curves. The higher fill factor (FF) of the MoOx-based device also suggests an improved charge collection efficiency compared to the cells with PEDOT:PSS. As for SHJ solar cells, we show that MoOx offers the means for dopant-free hole collection with both p-type and n-type Si wafers. In the present comparison over planar test structures with Ag back reflecting electrodes, we observe an efficiency gain of approximately 1% absolute against a baseline with a conventional p-type amorphous silicon hole collector. The gain is linked to the increased VOC, which is likely due to the reduced recombination at the Si wafer. [ABSTRACT FROM AUTHOR]