Rear interface engineering of hybrid organic-silicon nanowire solar cells via blade coating.

In this work, we investigate blade-coated organic interlayers at the rear surface of hybrid organic-silicon photovoltaics based on two small molecules: Tris(8-hydroxyquinolinato) aluminium (Alq(3)) and 1,3-bis(2-(4-tert-butylphenyl)-1,3,4-oxadiazol-5-yl) benzene (OXD-7). In particular, soluble Alq(3) resulting in a uniform thin film with a root-mean-square roughness < 0.2nm is demonstrated for the first time. Both devices with the Alq(3) and OXD-7 interlayers show notable enhancement in the open-circuit voltage and fill-factor, leading to a net efficiency increase by over 2% from the reference, up to 11.8% and 12.5% respectively. The capacitance-voltage characteristics confirm the role of the small-molecule interlayers resembling a thin interfacial oxide layer for the Al-Si Schottky barrier to enhance the built-in potential and facilitate charge transport. Moreover, the Alq(3) interlayer in optimized devices exhibits isolated phases with a large surface roughness, in contrast to the OXD-7 which forms a continuous uniform thin film. The distinct morphological differences between the two interlayers further suggest different enhancement mechanisms and hence offer versatile functionalities to the advent of hybrid organic-silicon photovoltaics.

One-step, room-temperature synthesis of glutathione-capped iron-oxide nanoparticles and their application in in vivo T1-weighted magnetic resonance imaging.

The room-temperature, aqueous-phase synthesis of iron-oxide nanoparticles (IO NPs) with glutathione (GSH) is reported. The simple, one-step reduction involves GSH as a capping agent and tetrakis(hydroxymethyl)phosphonium chloride (THPC) as the reducing agent; GSH is an anti-oxidant that is abundant in the human body while THPC is commonly used in the synthesis of noble-metal clusters. Due to their low magnetization and good water-dispersibility, the resulting GSH-IO NPs, which are 3.72 ± 0.12 nm in diameter, exhibit a low r2 relaxivity (8.28 mm(-1) s(-1)) and r2/r1 ratio (2.28)--both of which are critical for T1 contrast agents. This, together with the excellent biocompatibility, makes these NPs an ideal candidate to be a T1 contrast agent. Its capability in cellular imaging is illustrated by the high signal intensity in the T1-weighted magnetic resonance imaging (MRI) of treated HeLa cells. Surprisingly, the GSH-IO NPs escape ingestion by the hepatic reticuloendothelial system, enabling strong vascular enhancement at the internal carotid artery and superior sagittal sinus, where detection of the thrombus is critical for diagnosing a stroke. Moreover, serial T1- and T2-weighted time-dependent MR images are resolved for a rat's kidneys, unveiling detailed cortical-medullary anatomy and renal physiological functions. The newly developed GSH-IO NPs thus open a new dimension in efforts towards high-performance, long-circulating MRI contrast agents that have biotargeting potential.

Antiferromagnetic iron nanocolloids: a new generation in vivo T1 MRI contrast agent.

A novel T1 agent, antiferromagnetic α-iron oxide-hydroxide (α-FeOOH) nanocolloids with a diameter of 2-3 nm, has been successfully prepared. These nanocolloids, together with a post synthetic strategy performed in mesoporous silica, are a great improvement over the low T1-weighted contrast common in traditional magnetic silica nanocomposites. The intrinsic antiferromagnetic goethite (α-FeOOH) shows very low magnetization (M(z)) of 0.05 emu g(-1) at H = 2 T at 300 K (0.0006 emu g(-1) for FeOOH/WMSN-PEG), which is 2 orders of magnitude smaller than any current ultrasmall iron oxide NPs (>5 emu g(-1)) reported to date, hence ensuring the low r2 (∝ Mz) (7.64 mM(-1) s(-1)) and r2/r1 ratio (2.03) at 4.7 T. These biodegradable α-FeOOH nanocolloids also demonstrate excellent in vitro cellular imaging and in vivo MR vascular and urinary trace imaging capability with outstanding biocompatibility, which is exceptionally well secreted by the kidney and not the liver as with most nanoparticles, opening up a new avenue for designing powerful antiferromagnetic iron T1 contrast agents.

Self-amplitude and self-phase modulation of the charcoal mode-locked erbium-doped fiber lasers.

With the intra-cavity nano-scale charcoal powder based saturable absorber, the 455-fs passive mode-locking of an L-band erbium-doped fiber laser (EDFL) is demonstrated. The size reduction of charcoal nano-particle is implemented with a simple imprinting-exfoliation-wiping method, which assists to increase the transmittance up to 0.91 with corresponding modulation depth of 26%. By detuning the power gain from 17 to 21 dB and cavity dispersion from -0.004 to -0.156 ps² of the EDFL, the shortening of mode-locked pulsewidth from picosecond to sub-picosecond by the transformation of the pulse forming mechanism from self-amplitude modulation (SAM) to the combining effect of self-phase modulation (SPM) and group delay dispersion (GDD) is observed. A narrower spectrum with 3-dB linewidth of 1.83-nm is in the SAM case, whereas the spectral linewidth broadens to 5.86 nm with significant Kelly sideband pair can be observed if the EDFL enters into the SPM regime. The mode-locking mechanism transferred from SAM to SPM/GDD dominates the pulse shortening procedure in the EDFL, whereas the intrinsic defects in charcoal nano-particle only affect the pulse formation at initial stage. The minor role of the saturable absorber played in the EDFL cavity with strongest SPM is observed.

Application of F4TCNQ doped spiro-MeOTAD in high performance solid state dye sensitized solar cells.

Amid the investigation of solid-state dye-sensitized solar cells (SDSSCs), it was found that the incorporation of F4TCNQ into the solid hole-transporting materials (HTMs) spiro-MeOTAD forms a spiro-MeOTAD/F4TCNQ (strong electron acceptor) polaron charge-transfer complex. Careful examination indicates that the formation of the polaron charge-transfer complex not only facilitates the conductivity of HTMs but also inhibits the charge recombination across the interface of the heterojunction, i.e. photoanode/HTMs and/or counter electrode/HTMs. As a result, the performance of SDSSCs has been markedly improved by using the organic dye A2-F. At AM1.5 illumination the short circuit current densities J(SC) increase from 8.29 mA cm(-2) (w/o F4TCNQ) to 10.95 mA (w/F4TCNQ), accompanied by a 20% increase of the overall power conversion efficiency, η, from 4.55% to 5.44%.

Tumor pH-functionalized and charge-tunable nanoparticles for the nucleus/cytoplasm-directed delivery of oxaliplatin and miRNA in the treatment of head and neck cancer.

Prospective tumor pH-responsive and charge-convertible nanoparticles have been utilized to reduce side effects and improve the active tumor-targeting ability and nuclear/cytoplasmic localization of chemo- and gene therapeutics for the treatment of head and neck cancer (HNC). Oxaliplatin (Oxa) is a third-generation platinum compound that prevents DNA replication. miR-320 may regulate cancer cell apoptosis, resistance, and progression. Innovative nanoparticles incorporating miR-320 and Oxa were modified with a ligand, cell-penetrating peptide, and nucleus-targeted peptide. The nanoparticles were coated with a charge/size-tunable shield to prevent peptide degradation and decoated at acidic tumor sites to expose peptides for active targeting. Results indicated that the designed nanoparticles exhibited a uniform size and satisfactory drug encapsulation efficiency. The nanoparticles displayed the pH-responsive release and uptake of Oxa and miR-320 into human tongue squamous carcinoma SAS cells. The nanoparticles successfully delivered Oxa and miR-320 to the nucleus and cytoplasm, respectively. This work is the first to demonstrate the concurrent intracellular modulation of the NRP1/Rac1, PI3K/Akt/mTOR, GSK-3ß/FOXM1/ß-catenin, P-gp/MRPs, KRAS/Erk/Oct4/Yap1, and N-cadherin/Vimentin/Slug pathways to inhibit the growth, progression, and multidrug resistance of cancer cells. In SAS-bearing mice, co-treatment with Oxa- and miR-320-loaded nanoparticles exhibited superior antitumor efficacy and remarkably decreased Oxa-associated toxicities. The nucleus/cytoplasm-localized nanoparticles with a tumor pH-sensitive and size/charge-adjustable coating may be a useful combinatorial spatiotemporal nanoplatform for nucleic acids and chemotherapeutics to achieve maximum therapeutic safety and efficacy against HNC. STATEMENT OF SIGNIFICANCE: Innovative nanoparticles incorporating miR-320 and oxaliplatin were modified with a ligand, cell-penetrating peptide, and nucleus-targeted peptide. The tumor pH-sensitive and charge/size-adjustable shield of polyglutamic acid-PEG protected against peptide degradation during systemic circulation. This work represents the first example of the concurrent intracellular modulation of the NRP1/Rac1, PI3K/Akt/mTOR, GSK-3ß/FOXM1/ß-catenin, P-gp/MRPs, KRAS/Erk/Oct4/Yap1, and N-cadherin/Vimentin/Slug pathways to inhibit cancer cell growth, cancer cell progression, and multidrug resistance simultaneously. The versatile nanoparticles with a tumor pH-functionalized coating could deliver chemotherapeutics and miRNA to the nucleus/cytoplasm. The nanoparticles successfully reduced chemotherapy-associated toxicities and maximized the antitumor efficacy of combinatorial therapy against head and neck cancer.

pH-controlled stacking direction of the ß-strands in peptide fibrils.

Peptides provide a framework for generating functional biopolymers. In this study, the pH-dependent structural changes in the 21-29 fragment peptide of ß2-microglobulin (ß2m21-29) during self-aggregation, i.e., the formation of an amyloid fibril, were discussed. The ß-sheet structures formed during parallel stacking under basic conditions (pH ≥ 7.7) adopted an anti-parallel stacking configuration under acidic conditions (pH ≤ 7.6). The parallel and anti-parallel ß-sheets existed separately at the intermediate pH (pH = 7.6-7.7). These results were attributed to the rigidity of the ß-sheets in the fibrils, which prevented the stable hydrogen bonding interactions between the parallel and anti-parallel ß-sheet moieties. This observed pH dependence was ascribed to two phenomena: (i) the pH-dependent collapse of the ß2m21-29 fibrils, which consisted of 16 ± 3 anti-parallel ß-sheets containing a total of 2000 ß-strands during the deprotonation of the NH3+ group (pKa = 8.0) of the ß-strands that occurred within 0.7 ± 0.2 strands of each other and (ii) the subsequent formation of the parallel ß-sheets. We propose a framework for a functional biopolymer that could alternate between the two ß-sheet structures in response to pH changes.

PEG-coated nanoparticles detachable in acidic microenvironments for the tumor-directed delivery of chemo- and gene therapies for head and neck cancer.

Background: Head and neck cancer (HNC) is a major cause of morbidity and mortality and has a poor treatment outcome. Irinotecan, a topoisomerase-I inhibitor, induces cell death by decreasing the religation of double-strand DNA. However, epithelial-mesenchymal transition (EMT), therapy resistance, and systemic toxicity caused by available antineoplastic agents hinder the efficacy and safety of HNC treatment. Chemotherapy combined with gene therapy shows potential application in circumventing therapy resistance and EMT. miR-200 exerts a remarkable suppressing effect on EMT-associated genes. Herein, liposomes and solid lipid nanoparticles (SLNs) modified with a pH-sensitive, self-destructive polyethylene glycol (PEG) shell and different peptides were designed as irinotecan and miR-200 nanovectors to enhance tumor-specific accumulation. These peptides included one ligand targeting the angiogenic tumor neovasculature, one mitochondrion-directed apoptosis-inducing peptide, and one cell-penetrating peptide (CPP) with high potency and selectivity toward cancer cells. Methods: Physicochemical characterization, cytotoxicity analysis, cellular uptake, regulation mechanisms, and in vivo studies on miR-200- and irinotecan-incorporated nanoparticles were performed to identify the potential antitumor efficacy and biosafety issues involved in HNC treatment and to elucidate the underlying signaling pathways. Results: We found that the cleavable PEG layer responded to low extracellular pH, and that the CPP and targeting peptides were exposed to improve the uptake and release of miR-200 and irinotecan into HNC human tongue squamous carcinoma (SAS) cells. The apoptosis of SAS cells treated with the combinatorial therapy was significantly induced by regulating various pathways, such as the Wnt/ß-catenin, MDR, and EMT pathways. The therapeutic efficacy and safety of the proposed co-treatment outperformed the commercially available Onivyde and other formulations used in a SAS tumor-bearing mouse model in this study. Conclusion: Chemotherapy and gene therapy co-treatment involving pH-sensitive and targeting peptide-modified nanoparticles may be an innovative strategy for HNC treatment.

The effects of fluorine-contained molecules on improving the polymer solar cell by curing the anomalous S-shaped I-V curve.

In this study, we investigate the effects of fluorinated poly(3,4-ethylene dioxythiophene):poly(styrenesulfonate) buffer layer on the performance of polymer photovoltaic cells. We demonstrate for the first time, the deterioration of the device performance can be effectively mended by modifying the interface between the active layer and buffer layer with heptadecafluoro-1,1,2,2-tetra-hydro-decyl trimethoxysilane (PFDS) and perfluorononane. Device performance shows a substantial enhancement of short-circuit current from 7.90 to 9.39 mA/cm(2) and fill factor from 27% to 53%. The overall device efficiency was improved from 0.98% to 3.12% for PFDS modified device. The mechanism of S-shape curing is also discussed. In addition, the stability of modified devices shows significant improvement than those without modification. The efficiency of the modified devices retains about half (1.88%) of its initial efficiency (4.1%) after 30 d compared to the unmodified ones (0.61%), under air atmosphere.

High-efficiency small-molecule-based organic light emitting devices with solution processes and oxadiazole-based electron transport materials.

We demonstrate high-efficiency small-molecule-based white phosphorescent organic light emitting diodes (PHOLEDs) by single-active-layer solution-based processes with the current efficiency of 17.3 cdA(-1) and maximum luminous efficiency of 8.86 lmW(-1) at a current density of 1 mA cm(-2). The small-molecule based emitting layers are codoped with blue and orange phosphorescent dyes. We show that the presence of CsF/Al at cathodes not only improves electron transport in oxadiazole-containing electron transport layers (ETLs), but also facilitates electron injection through the reacted oxadiazole moiety to reduce interface resistance, which results in the enhancement of current efficiency. By selecting oxadiazole-based materials as ETLs with proper electron injection layer (EIL)/cathode structures, the brightness and efficiency of white PHOLEDs are significantly improved.