Hydrogel Scaffolds of Amphiphilic and Acidic β‐Sheet Peptides

Amphiphilic and acidic β‐sheet‐forming peptides (AAβPs) having the sequence Pro‐Y‐(Z‐Y)₅‐Pro, Y = Glu or Asp and Z = Phe or Leu may assemble into hydrogel structures at near neutral pH values, several units higher than the intrinsic pKa of their acidic amino acid side chains. The bottom‐to‐top design strategy enables the rationally supported association between the peptides' amino acids composition and bulk pH hydrogelation. Hydrogen bonds between the acidic amino acids side chains in the β‐sheet structure are found to contribute substantially to the stabilization of AAβPs hydrogels. The negatively charged peptides are also found to form gels at lower concentration in presence of calcium ions. Bone forming cells may be cultured on two‐dimensional films of AAβPs hydrogels that form at physiological pH values as well as within three dimensional hydrogel matrices. These acidic‐rich peptides hydrogels may become advantageous in applications related to engineering of mineralized tissues providing controllable, multifunctional calcified scaffolds to affect both the biological activity and the inorganic mineralization.     

Cationic Block Copolymer Nanoparticles with Tunable DNA Affinity for Treating Rheumatoid Arthritis

A high concentration of cell‐free DNA (cfDNA) in joints is considered a disease causative agent of rheumatoid arthritis (RA) and cfDNA scavenging has been regarded as an efficient therapeutic avenue. Cationic polymers can hamper progression of joint inflammation in a rat model of RA by scavenging cfDNA; however, they may cause systemic toxicity due to the strong positive charges. To reduce the toxicity, herein a library of cationic nanoparticles (cNPs) of block copolymer micelles is developed and the effects of structure and surface composition on cNP efficacy to bind nucleic acids, toxicity, and therapeutic activity on a collagen induced arthritis (CIA) rat model of RA are assessed. The library includes cNPs with a homoshell from poly(lactic‐co‐glycolic acid)‐block‐poly(2‐(dimethylamino)ethyl methacrylate) (PLGA‐b‐PDMA) block copolymers and cNPs with a mixed shell of poly(ethylene glycol) (PEG) and PDMA by coself‐assembling PLGA‐b‐PDMA and PLGA‐b‐PEG block copolymers. Relatively to the homoshell cNPs, introduction of PEG segments translates into a lower DNA binding efficacy while preserving ability to hamper joint inflammation. Moreover, they show a greater accumulation and longer retention at the inflamed joints, allowing a lower administration frequency. In conclusion, this work shows that the therapeutic index of cationic materials can be tuned by introducing surface neutral moieties.     

Cross‐National Differences in Political Discussion: Can Political Systems Narrow Deliberation Gaps?

Even though many researchers devoted considerable attention to political discussion and its individual‐level antecedents and outcomes, insights are based on single‐country studies. Cross‐national variations were either never studied or implicitly equated to the U.S. context. This study integrates explanations from communication and comparative politics to test whether political system features (e.g., electoral competitiveness and multiple parties) affect the macrosupply of political information, and thus either amplify or diminish the effects of individual characteristics on discussion. Analyses of cross‐national data show system features correlate with greater discussion frequency and moderate the contribution of individual differences to discussion. The potential of systems to narrow gaps in mass public discussion and implications for future research are considered in conclusion.     

Encountering “Difference” in the Contemporary Public Sphere: The Contribution of the Internet to the Heterogeneity of Political Discussion Networks

This study explores the intersection of media use, political discussion, and exposure to political difference through a focus on how Internet use might affect the overall heterogeneity of people's political discussion networks. Advanced and tested herein is the inadvertency thesis, which theorizes that limitations of selective exposure processes combined with weakened social boundaries found in the online environment suggest that people may be exposed to at least some additional political difference online, if only inadvertently. Hierarchical regression and mediation analyses confirm that online political discussion (directly) and online news (directly and indirectly) bear small yet significant relationships to the overall heterogeneity of political discussion networks, and that partisanship moderates the relationship between online political discussion and political discussion network heterogeneity.     

Online Groups and Political Discourse: Do Online Discussion Spaces Facilitate Exposure to Political Disagreement?

To what extent do online discussion spaces expose participants to political talk and to cross‐cutting political views in particular? Drawing on a representative national sample of over 1000 Americans reporting participation in chat rooms or message boards, we examine the types of online discussion spaces that create opportunities for cross‐cutting political exchanges. Our findings suggest that the potential for deliberation occurs primarily in online groups where politics comes up only incidentally, but is not the central purpose of the discussion space. We discuss the implications of our findings for the contributions of the Internet to cross‐cutting political discourse.     

Electrophosphorescent Devices Based on Cationic Complexes: Control of Switch‐on Voltage and Efficiency Through Modification of Charge Injection and Charge Transport

This paper reports an analysis of the properties of polymer light‐emitting devices (PLEDs) doped with iridium complexes. Devices based on charged and neutral complexes doped into poly(vinylcarbazole) (PVK) are presented, and the role of the ions and the charge‐transport properties of the complexes are discussed. In devices with the charged complexes, the concentration of the complex is found to have a profound effect on both the switch‐on voltage and the efficiency. At higher doping concentrations the efficiency is increased and the switch‐on voltage decreased. The increase in efficiency and decrease in switch‐on voltage at higher dopant concentration are found to be due to an alternative charge transport path via the iridium dopant [Ir(bpy)]⁺ (bis(2‐phenylpyridine‐C²,N′)(2,2′‐bipyridine)iridium hexafluorophosphate). However, at lower concentrations the complex becomes an electron trap and the efficiency is reduced. The devices are found to be significantly less efficient than those with neutral complexes. This difference is attributed to the ionic content and the charge trapping properties of the charged complexes. The low efficiency of the charged‐complex‐based devices could be overcome by utilizing a hole‐blocking layer; devices with efficiencies as high as 23 cd A^–1 were obtained.     

Reinforcement of the Political Self Through Selective Exposure to Political Messages

The idea that recipients prefer messages that reinforce preexisting attitudes and self‐perceptions has pervaded much communication research, but effects of selective exposure are rarely examined. This 2‐session experiment (n = 157) investigates such effects. The first session presented computerized questions on 12 political issue attitudes and political self‐concept. Accessibility data were collected based on response times. In the second session, participants browsed through an online magazine including 4 of the 12 issues, each issue being covered by 2 articles featuring opposing viewpoints. Selective exposure was logged and categorized as attitude‐consistent or counterattitudinal. Finally, a questionnaire repeated measures for attitudes and self‐concept. The results show that participants preferred attitude‐consistent over counterattitudinal messages, which strengthened the political self‐concept through increased accessibility.     

Of Attitudes and Engagement: Clarifying the Reciprocal Relationship Between Civic Attitudes and Political Participation

In this essay, we draw on broader psychological theories of the attitude–behavior relationship to postulate specific reciprocal patterns of causality between the civic attitudes and forms of political and civic engagement featured in contemporary political communication research. We then examine the extent of these reciprocal relationships with a 2‐wave panel survey of 2,872 Pacific Northwest residents. Spanning the 2004 elections, structural equation modeling of the panel data shows complex reciprocal causal paths between political/civic attitudes (internal and external efficacy and civic pride and faith) and a range of political and civic behaviors (voting, political action, media use, political/community talk, and group involvement). The conclusion suggests how to conceptualize these variables and model their relationships in future research.     

High Efficiency White Organic Light‐Emitting Devices Incorporating Yellow Phosphorescent Platinum(II) Complex and Composite Blue Host

A new class of charge neutral, strongly luminescent cyclometalated platinum(II) complexes supported by dianionic tetradentate ligand are synthesized. One of these platinum(II) complexes, Y‐Pt , displays a high photoluminescence quantum yield of 86% and electroluminescence efficacy (η_power) of up to 52 lm W^?1, and is utilized as a yellow phosphorescent dopant in the fabrication of white organic light‐emitting devices (WOLEDs). WOLEDs based on conventional structures with yellow emission from Y‐Pt in combination with blue emission from bis(4,6‐difluorophenyl‐pyridinato‐N,C²′) (picolinate) iridium(III) (FIrpic) show a total η_power of up to 31 lm W^?1. A two‐fold increase in η_power by utilizing a modified WOLED structure comprising of a composite blue host is realized. With this modified device structure, the total η_power and driving voltage at a luminance of 1000 cd m^?2 can be improved to 61 lm W^?1 and 7.5 V (i.e., 10 V for control devices). The performance improvement is attributed to an effectively broaden exciton formation‐recombination zone and alleviation of localized exciton accumulation within the FIrpic‐doped composite host for reduced triplet‐triplet annihilation, yielding blue light‐emission with enhanced intensity. The modified device structure can also adopt a higher concentration of Y‐Pt towards its optimal value, leading to WOLEDs with high efficiency.     

SEP calculations for coherent M‐ary FSK in different fading channels with MRC diversity

In this paper, the authors derive symbol error probability (SEP) expressions for coherent M‐ary frequency shift keying (MFSK) modulation schemes in multipath fading channels. The multipath or small‐scale fading process is assumed to be slow and frequency non‐selective. In addition, the channel is also subjected to the usual degradation caused by the additive white Gaussian noise (AWGN). Different small‐scale fading statistics such as Rayleigh, Rician (Nakagami‐n), Hoyt (Nakagami‐q), and Nakagami‐m have been considered to portray diverse wireless environments. Further, to mitigate fading effects through space diversity, the receiver front‐end is assumed to be equipped with multiple antennas. Independent and identically distributed (IID) as well as uncorrelated signal replicas received through all these antennas are combined with a linear combiner before successive demodulation. As the detection is coherent in nature and thus involves phase estimation, optimum phase‐coherent combining algorithms, such as predetection maximal ratio combining (MRC), may be used without any added complexity to the receiver. In the current text, utilizing the alternate expressions for integer powers (1≤n≤4) of Gaussian Q function, SEP values of coherent MFSK are obtained through moment generating function (MGF) approach for all the fading models (with or without MRC diversity) described above. The derived end expressions are composed of finite range integrals, which can be numerically computed with ease, dispenses with the need of individual expressions for different M, and gives exact values up to M=5. When the constellation size becomes bigger (M≥6), the same SEP expressions provide a quite realistic approximation, much tighter than the bounds found in previous literatures. Error probabilities are graphically displayed for each fading model with different values of constellation size M, diversity order L, and for corresponding fading parameters (K, q, or m). To validate the proposed approximation method extensive Monte‐Carlo simulations were also performed, which show a close match with the analytical results deduced in the paper. Both these theoretical and simulation results offer valuable insight to assess the efficacy of relatively less studied coherent MFSK in the context of the optimum modulation choice in wireless communication. Copyright © 2010 John Wiley & Sons, Ltd.     

New Conjugated Ladder Polymer Containing Carbazole Moieties

A new ladder polymer incorporating a polar carbazole group within the main chain, ladder‐type poly(para‐phenylene carbazole), LPPPC, was synthesized and characterized by luminescence techniques. Its properties are compared to that of the well‐known methyl‐substituted ladder‐type poly(para‐phenylene), MeLPPP. The results obtained evidence a very low energetic disorder in this new polymer, presumably due to its near‐perfect intrachain structure and low content of defects. It was found that although the density of states (DOS) distribution for neutral excitations is narrower than in MeLPPP, the manifold of charge‐transporting localized states is substantially more energetically disordered due to important dipolar disorder contributions.     

Polycationic Synergistic Antibacterial Agents with Multiple Functional Components for Efficient Anti‐Infective Therapy

Multifunctional antibacterial photodynamic therapy is a promising method to combat regular and multidrug‐resistant bacteria. In this work, eosin Y (EY)‐based antibacterial polycations (EY‐QEGED? R, R = ? CH₃ or ? C₆H₁₃) with versatile types of functional components including quaternary ammonium, photosensitizer, primary amine, and hydroxyl species are readily synthesized based on simple ring‐opening reactions. In the presence of light irradiation, such antibacterial polymers exhibit high antibacterial efficiency against both Escherichia coli and Staphylococcus aureus. In particular, EY‐QEGED? R elicits a remarkable synergistic antibacterial activity owing to the combined photodynamic and quaternary ammonium antibacterial effects. Due to its rich primary amine groups, EY‐QEGED? R also can be readily coated on different substrates, such as glass slides and nonwoven fabrics via an adhesive layer of polydopamine. The resultant surface coating of EY‐QEGED? CH₃ (s‐EY‐QEGED? CH₃) produces excellent in vitro antibacterial efficacy. The plentiful hydroxyl groups impart s‐EY‐QEGED? CH₃ with potential antifouling capability against dead bacteria. The antibacterial polymer coatings also demonstrate low cytotoxicity and good hemocompatibility. More importantly, s‐EY‐QEGED? CH₃ significantly enhances in vivo therapeutic effects on an infected rat model. The present work provides an efficient strategy for the rational design of high‐performance antibacterial materials to fight biomedical device‐associated infections.     

Electropolymerization of a Bifunctional Ionic Liquid Monomer Yields an Electroactive Liquid‐Crystalline Polymer

The preparation and polymerization of a bifunctional imidazolium‐based ionic liquid (IL) monomer that incorporates both a vinyl group and a thiophene moiety is reported. Potentiodynamic electropolymerization of the monomer produces an optically birefringent polymer film that strongly adheres to the electrode surface. Fourier transform IR spectroscopy shows that polymerization occurs through both the vinyl and thienyl groups. Cylic voltammetry (CV) is used to determine the polymer oxidation potential (1.66 V) and electrochemical bandgap, E_g, of 2.45 eV. The polymer exhibits electrochromism, converting from yellow in the neutral form (λ_max = 380 nm) to blue in the polaronic state at 0.6 V (λ_max = 672 nm) and to blue‐grey in the bipolaronic state at 1.2 V (λ_max > 800 nm). Topographic atomic force microscopy (AFM) images reveal isolated (separated) fibrils. Grazing‐incidence small‐angle X‐ray scattering (GISAXS) studies indicate a lamellar structure with a lattice spacing of 3.2 nm. Wide‐angle X‐ray diffraction (WAXD) studies further suggest that the polymerized thiophene sheets are oriented perpendicular to the polymerized vinylimidazolium. The electrical conductivity, as determined by four‐probe dc conductivity measurements was found to be 0.53 S cm^?1 in the neutral form and 2.36 S cm^?1 in the iodine‐doped state, values higher than typically observed for polyalkylthiophenes. The structural ordering is believed to contribute to the observed enhancement of the electrical conductivity.     

Self‐Assembled Nanoparticles with Dual Effects of Passive Tumor Targeting and Cancer‐Selective Anticancer Effects

Nanoparticular drug delivery systems may help to overcome the limitations of conventional chemotherapy. They have been reported to improve the specificity of distribution, the bioavailability, and the solubility of drugs, as well as the duration of drug efficacy, and helping to overcome multidrug resistance. Although various polymeric nanoparticles have been developed for delivery of anticancer agents, most nanoparticles still focus on solubilizing drugs, improving targeting ability, and reducing side effects. In particular, targeting to the tumor is typically improved through passive or active targeting. Despite great achievements in both strategies, yet to be resolved are issues of toxicity in normal cells and enhancement of tumor‐specificity. A new approach combining the dual strategies of passive tumor targeting and cancer‐selective efficacy is proposed. Recombinant human gelatin conjugated with lipoic acid (rHG‐LA) developed in this study forms nanoparticles spontaneously in aqueous solution and encapsulates alpha‐tocopheryl succinate (α‐TOS), a well‐known cancer‐selective apoptosis‐inducing agent, within a hydrophobic core during the self‐assembly. This study describes the promising applicability of α‐TOS‐loaded rHG‐LA nanoparticles with passive targeting ability and cancer‐specificity.     

Fluorine Segregation Controls the Solid‐State Organization and Electronic Properties of Ni and Au Dithiolene Complexes: Stabilization of a Conducting Single‐Component Gold Dithiolene Complex

Electrooxidation of the nickel dithiolene complex [Ni(F₂pdt)₂]^–· (F₂pdt^2‐: 6,6‐difluoro‐6,7‐dihydro‐5H‐[1,4]dithiepine‐2,3‐dithiolato) affords the corresponding neutral complex [Ni(F₂pdt)₂]⁰ whose layered structure is highly reminiscent, albeit not isostructural, of that of the isosteric fluorinated bis(propylenedithio)tetrathiafulvalene and characterized by a segregation of the fluorinated moieties into fluorous bilayers. The gold neutral complex [Au(F₂pdt)₂]^·, which is isostructural with the fluorinated bis(propylenedithio)tetrathiafulvalene, was prepared by electrocrystallization of the [n‐Bu₄N][Au(F₂pdt)₂] salt. [Au(F₂‐pdt)₂]^· is a semiconductor with high room temperature conductivity. The origin of this semiconducting behavior as well as possible guidelines in order to realize metallic conductivity in gold dithiolene neutral molecular solids are discussed.     

Anode Interfacial Tuning via Electron‐Blocking/Hole‐Transport Layers and Indium Tin Oxide Surface Treatment in Bulk‐Heterojunction Organic Photovoltaic Cells

The effects of anode/active layer interface modification in bulk‐heterojunction organic photovoltaic (OPV) cells is investigated using poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and/or a hole‐transporting/electron‐blocking blend of 4,4′‐bis[(p‐trichlorosilylpropylphenyl)‐phenylamino]biphenyl (TPDSi₂) and poly[9,9‐dioctylfluorene‐co‐N‐[4‐(3‐methylpropyl)]‐diphenylamine] (TFB) as interfacial layers (IFLs). Current–voltage data in the dark and AM1.5G light show that the TPDSi₂:TFB IFL yields MDMO‐PPV:PCBM OPVs with substantially increased open‐circuit voltage (V_oc), power conversion efficiency, and thermal stability versus devices having no IFL or PEDOT:PSS. Using PEDOT:PSS and TPDSi₂:TFB together in the same cell greatly reduces dark current and produces the highest V_oc (0.91 V) by combining the electron‐blocking effects of both layers. ITO anode pre‐treatment was investigated by X‐ray photoelectron spectroscopy to understand why oxygen plasma, UV ozone, and solvent cleaning markedly affect cell response in combination with each IFL. O₂ plasma and UV ozone treatment most effectively clean the ITO surface and are found most effective in preparing the surface for PEDOT:PSS deposition; UV ozone produces optimum solar cells with the TPDSi₂:TFB IFL. Solvent cleaning leaves significant residual carbon contamination on the ITO and is best followed by O₂ plasma or UV ozone treatment.     

Quaternized Silicon Nanoparticles with Polarity‐Sensitive Fluorescence for Selectively Imaging and Killing Gram‐Positive Bacteria

With the emergence of antibiotic resistance, developing new antibiotics and therapies for combating bacterial infections is urgently needed. Herein, a series of quaternized fluorescent silicon nanoparticles (SiNPs) are facilely prepared by the covalent reaction between amine‐functionalized SiNPs and carboxyl‐containing N‐alkyl betaines. It is found that the bactericidal efficacy of these quaternized SiNPs increases with the length of the N‐alkyl chain, and SiNPs conjugated with N,N‐dimethyl‐N‐octadecylbetaine (BS‐18), abbreviated as SiNPs‐C₁₈, show the best antibacterial effect, whose minimum inhibitory concentrations for Gram‐positive bacteria are 1–2 μg mL^?1. In vivo tests further confirm that SiNPs‐C₁₈ have excellent antibacterial efficacy and greatly reduce bacterial load in the infectious sites. The SiNPs‐C₁₈ exhibit low cytotoxicity toward mammalian cells (including normal liver and lung cells, red blood cells, and macrophages), enabling them to be useful for clinical applications. Besides, the quaternized SiNPs exhibit polarity‐dependent fluorescence emission property and can selectively image Gram‐positive bacteria, thereby providing a simple method to successfully differentiate Gram‐positive and Gram‐negative bacteria. The present work represents the first example that successfully turns fluorescent SiNPs into metal‐free NP‐based antibiotics with simultaneous bacterial imaging and killing capability, which broadens the applications of fluorescent SiNPs and advances the development of novel antibacterial agents.     

Long‐term transient and metastable effects in cadmium telluride photovoltaic modules

Thin‐film cadmium telluride (CdTe) photovoltaic (PV) technology is poised to begin making significant contributions and impact on terrestrial, electric power generation. However, some outstanding issues such as stability and transient behavior, and their impact on reliability and assessment of performance, remain to be thoroughly addressed, which has prompted some unease among PV industry integrators toward deploying this technology. We explore the issues of long‐term stability and transient behavior in the performance of CdTe modules herein, using data acquired from indoor light‐soaking studies. We find that measurement of current‐voltage parameters and their temperature coefficients are entangled with transient effects. Changes in module power depend on recent operating history, such as electrical bias, and can result in either artificially high or low performance. Both the open‐circuit voltage (V_OC) and fill factor (FF) are significantly impacted by metastable behavior that appears to linger for up to tens of hours, and we observe such increased transient effects after modules have undergone several hundred hours of light exposure. We present and analyze data measured under standard reporting conditions and actual operating conditions for six CdTe modules light‐exposed and stressed at 65°C nominal temperatures. Copyright © 2006 John Wiley & Sons, Ltd.     

Public Spheres in Interaction: Comment Sections of News Websites as Counterpublic Spaces

Research scrutinizing political talk online has been developed largely against the backdrop of deliberative discursive norms and considered political talk without a systematic analysis of surrounding mass‐mediated discourses. By contrast, this study operationalizes counterpublic theory as an alternative theoretical perspective and analyzes comments on news websites as a reaction to hegemonic mainstream public spheres. It juxtaposes a qualitative framing analysis of all articles about a new anti‐Euro party in devotedly pro‐European Germany published on 9 news websites in the week following the 2013 elections (n = 22) with a content analysis of all comments posted below these articles (n = 3,154). It finds counterpublic spheres differently shaped in comment sections of right‐ and left‐leaning, and tabloid and nontabloid, outlets. Consequences for democracy are discussed.     

Enhancement of Phosphorescence by Surface‐Plasmon Resonances in Colloidal Metal Nanoparticles: The Role of Aggregates

The spectroscopic and near‐field scanning optical microscopy (NSOM) studies of phosphorescent films doped with colloidal gold nanoparticles (NPs) are presented. Films with a high concentration of 2,3,7,8,12,13,17,18‐octaethyl‐21H,23H‐porphine platinum(II ) dispersed in a neutral polymer poly[(methyl methacrylate)‐co‐(ethyl acrylate)] demonstrate a twofold increase of the phosphorescence quantum yield after the addition of aggregated NPs. In materials doped with unaggregated particles, a decrease of the emission yield is observed. Theoretical modeling of the phosphorescence transients suggests a minimization of the triplet–triplet quenching owing to the presence of fast processes that decrease the concentration of chromophores in the excited state and may be both of radiative and non‐radiative origin. NSOM examination of the films reveals increased light emission around large NP clusters. This observation demonstrates significant enhancement of the spontaneous emission rates by the large aggregates, although unaggregated NPs introduce mostly phosphorescence quenching sites.