Effect of External Magnetic Field on Bulk Heterojunction Polymer Solar Cells.

Polymer solar cells (PSCs) with a bulk heterojunction (BHJ) device structure have incredible advantages, such as low-cost fabrication and flexibility. However, the power conversion efficiency (PCE) of BHJ PSCs needs to be further improved to realize their practical applications. In this study, boosted PCEs from PSCs based on BHJ composites incorporated with Fe3 O4 magnetic nanoparticles (MNPs), aligned by an external magnetic field (EMF), are reported. It is found that the coercive electric field within the Fe3 O4 MNPs generated by the EMF has a strong and positive influence on the charge generation, which results in a more than 10% increase in free charge carriers. Moreover, the coercive electric field speeds up the charge carrier transport and suppresses charge carrier recombination within PSCs. In addition, a shortened extraction time makes charge carriers more likely to make it to the electrodes. As a result, more than 15% enhancement in PCE is observed from the PSCs based on the BHJ composite incorporated with the Fe3 O4 MNPs and the EMF as compared with that based on the BHJ composite thin film. This work indicates that the incorporation of MNPs and the EMF is a facile way to enhance the PCEs of PSCs.

Origins of the Photocurrent Multiplication Effect in the Polythiophene-Based Photodetectors.

The photocurrent multiplication (PM) effect has been used to boost the device performance of polymer-based photodetectors (PDs), but its origin is rarely addressed. In this study, the origins of the PM effect in polymer PDs based on the P3HT:PC71 BM bulk heterojunction (BHJ) composite thin film, where P3HT is poly(3-hexylthiophene), and PC71 BM is [6,6]phenyl-C71 -butyric acid methyl ester, through both computational simulation and experimental investigation are reported. Systematic studies indicate that two key factors play an important role in the realization of the PM effect in polymer PDs. One factor is the work function of the metal electrode, and the other is the PC71 BM aggregations at the interface between the P3HT:PC71 BM BHJ composite thin film and the metal electrode. Moreover, the results from both experimental and computational simulation indicate that the values of the current density under light illumination minus the current density in the dark of polymer PDs are increased simultaneously along with the reduction of the thickness of the P3HT:PC71 BM BHJ composite thin film. The results provide an understanding of the PM effect in polymer PDs and guidance for the development of high-performance polymer PDs based on BHJ composite thin film.

Formulating Zwitterionic, Responsive Polymers for Designing Smart Soils.

The design of new remediation strategies and materials for treating saline-alkaline soils is of fundamental and practical importantance for many applications. Conventional soil remediation strategies mainly focus on the development of fertilizers or additives for water, nutrient, and heavy metal managements in soils, but they often overlook a soil sensing function for early detection of salinization/alkalization levels toward optimal and timely soil remediation. Here, new smart soils, structurally consisting of the upper signal soil and the bottom hygroscopic bed and chemically including zwitterionic, thermo-responsive poly(NIPAM-co-VPES) and poly(NIPAM-co-SBAA) aerogels in each soil layer are formulated. Upon salinization, the resultant smart soils exhibit multiple superior capacities for reducing the soil salinity and alkalinity through ion exchange, controlling the water cycling, modulating the degradation of pyridine-base ligands into water-soluble, nitrogenous salts-rich ingredients for soil fertility, and real-time monitoring salinized soils via pH-induced allochroic color changes. Further studies of plant growth in smart soils with or without salinization treatments confirm a synergy effect of soil remediation and soil sensing on facilitating the growth of plants and increasing the saline-alkaline tolerance of plants. The esign concept of smart soils can be further expanded for soil remediation and assessment.

Dual functionality of antimicrobial and antifouling of poly(N-hydroxyethylacrylamide)/salicylate hydrogels.

The emergence and reemergence of microbial infection demand an urgent response to develop effective biomaterials that prevent biofilm formation and associated bacterial infection. In this work, we have synthesized and characterized hybrid poly(N-hydroxyethylacrylamide) (polyHEAA)/salicylate (SA) hydrogels with integrated antifouling and antimicrobial capacities. The antifouling efficacy of polyHEAA hydrogels was examined via exposure to proteins, cells, and bacteria, while the antimicrobial activity of SA-treated polyHEAA hydrogels was investigated against both gram-negative Escherichia coli RP437 and gram-positive Staphylococcus epidermidis. The results showed that polyHEAA/SA hydrogels exhibited high surface resistance to protein adsorption, cell adhesion, and bacteria attachment. The polyHEAA hydrogels were also characterized by their water content and state of water, revealing a strong ability to contain and retain high nonfreezable water content. This work demonstrates that the hybrid polyHEAA/SA hydrogels can be engineered to possess both antifouling and antimicrobial properties, which can be used for different in vitro and in vivo applications against bacterial infection.

Colorimetric detection of DNA, small molecules, proteins, and ions using unmodified gold nanoparticles and conjugated polyelectrolytes.

We have demonstrated a novel sensing strategy employing single-stranded probe DNA, unmodified gold nanoparticles, and a positively charged, water-soluble conjugated polyelectrolyte to detect a broad range of targets including nucleic acid (DNA) sequences, proteins, small molecules, and inorganic ions. This nearly "universal" biosensor approach is based on the observation that, while the conjugated polyelectrolyte specifically inhibits the ability of single-stranded DNA to prevent the aggregation of gold-nanoparticles, no such inhibition is observed with double-stranded or otherwise "folded" DNA structures. Colorimetric assays employing this mechanism for the detection of hybridization are sensitive and convenient--picomolar concentrations of target DNA are readily detected with the naked eye, and the sensor works even when challenged with complex sample matrices such as blood serum. Likewise, by employing the binding-induced folding or association of aptamers we have generalized the approach to the specific and convenient detection of proteins, small molecules, and inorganic ions. Finally, this new biosensor approach is quite straightforward and can be completed in minutes without significant equipment or training overhead.

On the binding of cationic, water-soluble conjugated polymers to DNA: electrostatic and hydrophobic interactions.

Water-soluble, cationic conjugated polymer binds single-stranded DNA with higher affinity than it binds double-stranded or otherwise "folded" DNA. This stronger binding results from the greater hydrophobicity of single-stranded DNA. Upon reducing the strength of the hydrophobic interactions, the electrostatic attraction becomes the important interaction that regulates the binding between the water-soluble conjugated polymer and DNA. The different affinities between the cationic conjugated polymer and various forms of DNA (molecular beacons and its open state; single-stranded DNA and double-stranded DNA and single-stranded DNA and complex DNA folds) can be used to design a variety of biosensors.

Semiconducting polymer photodetectors with electron and hole blocking layers: high detectivity in the near-infrared.

Sensing from the ultraviolet-visible to the infrared is critical for a variety of industrial and scientific applications. Photodetectors with broad spectral response, from 300 nm to 1,100 nm, were fabricated using a narrow-band gap semiconducting polymer blended with a fullerene derivative. By using both an electron-blocking layer and a hole-blocking layer, the polymer photodetectors, operating at room temperature, exhibited calculated detectivities greater than 10(13) cm Hz(1/2)/W over entire spectral range with linear dynamic range approximately 130 dB. The performance is comparable to or even better than Si photodetectors.

Molecular simulations and understanding of antifouling zwitterionic polymer brushes.

Zwitterionic materials are an important class of antifouling biomaterials for various applications. Despite such desirable antifouling properties, molecular-level understanding of the structure-property relationship associated with surface chemistry/topology/hydration and antifouling performance still remains to be elucidated. In this work, we computationally studied the packing structure, surface hydration, and antifouling property of three zwitterionic polymer brushes of poly(carboxybetaine methacrylate) (pCBMA), poly(sulfobetaine methacrylate) (pSBMA), and poly((2-(methacryloyloxy)ethyl)phosporylcoline) (pMPC) brushes and a hydrophilic PEG brush using a combination of molecular mechanics (MM), Monte Carlo (MC), molecular dynamics (MD), and steered MD (SMD) simulations. We for the first time determined the optimal packing structures of all polymer brushes from a wide variety of unit cells and chain orientations in a complex energy landscape. Under the optimal packing structures, MD simulations were further conducted to study the structure, dynamics, and orientation of water molecules and protein adsorption on the four polymer brushes, while SMD simulations to study the surface resistance of the polymer brushes to a protein. The collective results consistently revealed that the three zwitterionic brushes exhibited stronger interactions with water molecules and higher surface resistance to a protein than the PEG brush. It was concluded that both the carbon space length between zwitterionic groups and the nature of the anionic groups have a distinct effect on the antifouling performance, leading to the following antifouling ranking of pCBMA > pMPC > pSBMA. This work hopefully provides some structural insights into the design of new antifouling materials beyond traditional PEG-based antifouling materials.

Design of salt-responsive and regenerative antibacterial polymer brushes with integrated bacterial resistance, killing, and release properties.

The development of smart materials and surfaces with multiple antibacterial actions is of great importance for both fundamental research and practical applications, but this has proved to be extremely challenging. In this work, we proposed to integrate salt-responsive polyDVBAPS (poly(3-(dimethyl(4-vinylbenzyl) ammonio)propyl sulfonate)), antifouling polyHEAA (poly(N-hydroxyethyl acrylamide)), and bactericidal TCS (triclosan) into single surfaces by polymerizing and grafting polyDVBAPS and polyHEAA onto the substrate in a different way to form two types of polyDVBAPS/poly(HEAA-g-TCS) and poly(DVBAPS-b-HEAA-g-TCS) brushes with different hierarchical structures, as confirmed by X-ray photoelectron spectroscopy (XPS), atom force microscopy (AFM), and ellipsometry. Both types of polymer brushes demonstrated their tri-functional antibacterial activity to resist bacterial attachment by polyHEAA, to release ∼90% of dead bacteria from the surface by polyDVBAPS, and to kill ∼90% of bacteria on the surface by TCS. Comparative studies also showed that removal of any component from polyDVBAPS/poly(HEAA-g-TCS) and poly(DVBAPS-b-HEAA-g-TCS) compromised the overall antibacterial performance, further supporting a synergistic effect of the three compatible components. More importantly, the presence of salt-responsive polyDVBAPS allowed both brushes to regenerate with almost unaffected antibacterial capacity for reuse in multiple kill-and-release cycles. The tri-functional antibacterial surfaces present a promising design strategy for further developing next-generation antibacterial materials and coatings for antibacterial applications.

Light-emitting devices based on ruthenium (II) bipyridine complexes coupled with cadmium sulfide nanoparticles.

The fabrication of a light-emitting device based on a composite consisting of cadmium sulfide nanoparticle, poly(vinylalcohol), and ruthenium 2,2'-bipyridyl complex is reported. The electroluminescence spectrum of this composite is similar to the combination of the emission from ruthenium complexes and cadmium sulfide. A stable electroluminescence at low threshold voltage (4 V), with a brightness of 680 cd/m2 and an external quantum efficiency of approximately 0.2% was achieved. it was demonstrated that the cadmium sulfide nanoparticles were able to improve the performance of the device and enhance the electron carrier mobility as compared to the device based on pure ruthenium complex.

Probing structure-antifouling activity relationships of polyacrylamides and polyacrylates.

We have synthesized two different polyacrylamide polymers with amide groups (polySBAA and polyHEAA) and two corresponding polyacrylate polymers without amide groups (polySBMA and polyHEA), with particular attention to the evaluation of the effect of amide group on the hydration and antifouling ability of these systems using both computational and experimental approaches. The influence of polymer architectures of brushes, hydrogels, and nanogels, prepared by different polymerization methods, on antifouling performance is also studied. SPR and ELISA data reveal that all polymers exhibit excellent antifouling ability to repel proteins from undiluted human blood serum/plasma, and such antifouling ability can be further enhanced by presenting amide groups in polySBAA and polyHEAA as compared to polySBMA and polyHEA. The antifouling performance is positively correlated with the hydration properties. Simulations confirm that four polymers indeed have different hydration characteristics, while all presenting a strong hydration overall. Integration of amide group with pendant hydroxyl or sulfobetaine group in polymer backbones is found to increase their surface hydration of polymer chains and thus to improve their antifouling ability. Importantly, we present a proof-of-concept experiment to synthesize polySBAA nanogels, which show a switchable property between antifouling and pH-responsive functions driven by acid-base conditions, while still maintaining high stability in undiluted fetal bovine serum and minimal toxicity to cultured cells. This work provides important structural insights into how very subtle structural changes in polymers can yield great improvement in biological activity, specifically the inclusion of amide group in polymer backbone/sidechain enables to obtain antifouling materials with better performance for biomedical applications.

Solution-processed Fe3O4 magnetic nanoparticle thin film aligned by an external magnetostatic field as a hole extraction layer for polymer solar cells.

We report, for the first time, the effect of a solution-processed Fe3O4 magnetic nanoparticle (MNP) thin film and a Fe3O4 MNP thin film aligned by an external magnetostatic field, used as a hole extraction layer (HEL), respectively, in polymer solar cells (PSCs). The thin film of a Fe3O4 MNP shows a smoother surface, better transparency, and higher electrical conductivity than that of a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) thin layer. Moreover, the thin film of a Fe3O4 MNP aligned by an external magnetostatic field possesses an enhanced electrical conductivity and lower internal series resistance, thus leading to greater than 13% enhancement in the power conversion efficiency of PSCs than those using a PEDOT:PSS thin film. It was also found that PSCs incorporated with a Fe3O4 MNP shows better stability compared with those using PEDOT:PSS as an anode buffer layer. These results demonstrated that utilization of a Fe3O4 MNP as a HEL in PSCs blazes a trail to achieve highly efficient and long-time-stable devices.

Biosensors from conjugated polyelectrolyte complexes.

A charge neutral complex (CNC) was formed in aqueous solution by combining an orange light emitting anionic conjugated polyelectrolyte and a saturated cationic polyelectrolyte at a 1:1 ratio (per repeat unit). Photoluminescence (PL) from the CNC can be quenched by both the negatively charged dinitrophenol (DNP) derivative, (DNP-BS(-)), and positively charged methyl viologen (MV(2+)). Use of the CNC minimizes nonspecific interactions (which modify the PL) between conjugated polyelectrolytes and biopolymers. Quenching of the PL from the CNC by the DNP derivative and specific unquenching on addition of anti-DNP antibody (anti-DNP IgG) were observed. Thus, biosensing of the anti-DNP IgG was demonstrated.