Medium Bandgap Polymers for Efficient Non-Fullerene Polymer Solar Cells-An In-Depth Study of Structural Diversity of Polymer Structure.

A series of medium bandgap polymer donors, named poly(1-(5-(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo [1,2-b:4,5-b']dithiophen-2-yl)thiophen-2-yl)-5-((4,5-dihexylthiophen-2-yl)methylene)-3-(thiophen-2-yl)-4H-cyclopenta[c]thiophene-4,6(5H)-dione) (IND-T-BDTF), poly(1-(5-(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo [1,2-b:4,5-b']dithiophen-2-yl)-4-hexylthiophen-2-yl)-5-((4,5-dihexylthiophen-2-yl)methylene)-3-(4-hexylthiophen-2-yl)-4H-cyclopenta[c]thiophene-4,6(5H)-dione (IND-HT-BDTF), and poly(1-(5-(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo [1,2-b:4,5-b']dithiophen-2-yl)-6-octylthieno [3,2-b]thiophen-2-yl)-5-((4,5-dihexylthiophen-2-yl)methylene)-3-(6-octylthieno [3,2-b]thiophen-2-yl)-4H-cyclopenta[c]thiophene-4,6(5H)-dione (IND-OTT-BDTF), are developed for non-fullerene acceptors (NFAs) polymer solar cells (PSCs). Three polymers consist of donor-acceptor building block, where the electron-donating fluorinated benzodithiophene (BDTF) unit is linked to the electron-accepting 4H-cyclopenta[c]thiophene-4,6(5H)-dione (IND) derivative via thiophene (T) or thieno [3,2-b]thiopene (TT) bridges. The absorption range of the polymer donors based on IND in this study shows 400~800 nm, which complimenting the absorption of Y6BO (600~1000 nm). The PSC's performances are also significantly impacted by the π-bridges. NFAs inverted type PSCs based on polymer donors and Y6BO acceptor are fabricated. The power conversion efficiency (PCE) of the device based on IND-OTT-BDTF reaches up to 11.69% among all polymers with a short circuit current of 26.37 mA/cm2, an open circuit voltage of 0.79 V, and a fill factor of 56.2%, respectively. This study provides fundamental information on the invention of new polymer donors for NFA-based PSCs.

Dual Stimuli-Responsive Vesicular Nanospheres Fabricated by Lipopolymer Hybrids for Tumor-Targeted Photodynamic Therapy.

Smart delivery system of photosensitizer chlorin e6 (Ce6) has been developed for targeted photodynamic therapy (PDT). Simple self-assemblies of the mixtures comprising soybean lecithin derived phosphatidylcholine (PC), phosphatidylethanolamine-poly(L-histidine)40 (PE-p(His)40), and folic acid (FA) conjugated phosphatidylethanolamine-poly(N-isopropylacrylamide)40 (PE-p(NIPAM)40-FA) in different ratios yield smart nanospheres characterized by (i) stable and uniform particle size (∼100 nm), (ii) positive surface charge, (iii) high hydrophobic drug (Ce6) loading efficiency up to 45%, (iv) covalently linked targeting moiety, (v) low cytotoxicity, and (vi) smartness showing p(His) block oriented pH and p(NIPAM) oriented temperature responsiveness. The Ce6-encapsulated vesicular nanospheres (Ce6@VNS) were used to confirm the efficiency of cellular uptake, intracellular distribution, and phototoxicity against KB tumor cells compared to free Ce6 at different temperature and pH conditions. The Ce6@VNS system showed significant photodynamic therapeutic efficiency on KB cells than free Ce6. A receptor-mediated inhibition study proved the site-specific delivery of Ce6 in targeted tumor cells.

The Electrical Properties for Phenolic Isocyanate-Modified Bisphenol-Based Epoxy Resins Comprising Benzoate Group.

Epoxy resin has been required to have a low dielectric constant (D(k)), low dissipation factor (Df), low coefficient of thermal expansion (CTE), low water absorption, high mechanical, and high adhesion properties for various applications. A series of novel phenolic isocyanate-modified bisphenol-based epoxy resins comprising benzoate group were prepared for practical electronic packaging applications. The developed epoxy resins showed highly reduced dielectric constants (D(k)-3.00 at 1 GHz) and low dissipation values (Df-0.014 at 1 GHz) as well as enhanced thermal properties.

Lipo-poly(L-histidine) hybrid materials with pH-sensitivity, intracellular delivery efficiency, and intrinsic targetability to cancer cells.

Biocompatible lipo-histidine hybrid materials conjugated with IR820 dye show pH-sensitivity, efficient intracellular delivery of doxorubicin (Dox), and intrinsic targetability to cancer cells. These new materials form highly uniform Dox-loaded nanosized vesicles via a self-assembly process showing good stability under physiological conditions. The Dox-loaded micelles are effective for suppressing MCF-7 tumors, as demonstrated in vitro and in vivo. The combined mechanisms of the EPR effect, active internalization, endosomal-triggered release, and drug escape from endosomes, and a long blood circulation time, clearly prove that the IR820 lipopeptide DDS is a safe theranostic agent for imaging-guided cancer therapy.

Anti-inflammatory potential of newly synthesized 4-[(butylsulfinyl)methyl]-1,2-benzenediol in lipopolysaccharide-stimulated BV2 microglia.

In this study, we investigated the anti-inflammatory effects of newly synthesized 4-[(butylsulfinyl)methyl]-1,2-benzenediol (SMBD) in lipopolysaccharide (LPS)-stimulated BV2 microglia and the subsequent signaling events. Following stimulation with LPS, elevated production of nitric oxide (NO) and prostaglandin E2 (PGE2) was detected in BV2 cells; however, SMBD pretreatment inhibited the production of NO and PGE2 through suppressing gene expression of inducible NO synthase (iNOS) and cyclooxygenase-2 (COX-2), respectively, at non-toxic concentrations. LPS-stimulated gene expression and production of interleukin (IL)-1ß and tumor necrosis factor (TNF)-α were also significantly reduced by SMBD. The anti-inflammatory effects of SMBD were associated with suppression of LPS-induced nuclear translocation of nuclear factor-kappa B (NF-κB), and phosphorylation of mitogen-activated protein kinases (MAPKs) and Akt, a phosphatidylinositol 3-kinase (PI3K) downstream effector. Therefore, the present results demonstrate that SMBD down-regulates inflammatory gene expression by inhibiting the activation of NF-κB through interference with the activation of MAPKs and PI3K/Akt signaling. Taken together, our data suggest that SMBD may have potential to be developed into an effective anti-inflammatory agent.

Fabrication of microspheres via solvent volatization induced aggregation of self-assembled nanomicellar structures and their use as a pH-dependent drug release system.

A series of oleamide derivatives, (C(18)H(34)NO)(2)(CH(2))(n) [n = 2 (1a), 3 (1b), 4 (1c), or 6 (1d); C(18)H(34)NO = oleic amide fragment] and (C(18)H(34)NO)(CH(2))(6)NH(2) (2), have been synthesized and their self-assembly is investigated in ethanol/water media. Self-assembly of 1a and 1b in ethanol/water (1/0.1 v/v) solution (5 mg mL(-1)) yields microspheres (MSs) with the average diameter ∼10 µm via a gradual temperature reduction and solvent volatilization process. Under the same self-assembly conditions, microrods (average diameter ∼6 µm and several tens of micrometers in length), micronecklace-like, and shape-irregular microparticles are formed from the self-assembly of 1c, 1d, and 2, respectively. The kinetics of evolution for their self-assemblies by dynamic light scattering technique and in situ observation by optical microscopy reveals that the microstructures formation is from a well-behaved aggregation of nanoscale micelles induced by solvent volatilization. The FT-IR and temperature-dependent (1)H-NMR spectra demonstrate the hydrogen bonding force and π-π stacking, which drove the self-assembly of all oleamide derivatives in ethanol/water. Among the fabricated microstructures, the MSs from 1a exhibit the best dispersity, which thus have been used as a scaffold for the in vitro release of doxorubicin. The results demonstrate a pH-sensitive release process, enhanced release specifically at low pH 5.2.

Easy synthesis of hierarchical carbon spheres with superior capacitive performance in supercapacitors.

An easy template-free approach to the fabrication of pure carbon microspheres has been achieved via direct pyrolysis of as-prepared polyaromatic hydrocarbons including polynaphthalene and polypyrene. The polyaromatics were synthesized from aromatic hydrocarbons (AHCs) using anhydrous zinc chloride as the Friedel-Crafts catalyst and chloromethyl methyl ether as a cross-linker. The experimental results show that the methylene bridges between phenyl rings generate a hierarchical porous polyaromatic precursor to form three-dimensionally (3D) interconnected micro-, meso-, and macroporous networks during carbonization. These hierarchical porous carbon aggregates of spherical carbon spheres exhibit faster ion transport/diffusion behavior and increased surface area usage in electric double-layer capacitors. Furthermore, micropores are present in the 3D interconnected network inside the cross-linked AHC-based carbon microspheres, thus imparting an exceptionally large, electrochemically accessible surface area for charge accumulation.

Dual stimuli-responsive poly(N-isopropylacrylamide)-b-poly(L-histidine) chimeric materials for the controlled delivery of doxorubicin into liver carcinoma.

A series of dual stimuli responsive synthetic polymer bioconjugate chimeric materials, poly(N-isopropylacrylamide)55-block-poly(L-histidine)n [p(NIPAM)55-b-p(His)n] (n=50, 75, 100, 125), have been synthesized by employing reversible addition-fragmentation chain transfer polymerization of NIPAM, followed by ring-opening polymerization of α-amino acid N-carboxyanhydrides. The dual stimuli responsive properties of the resulting biocompatiable and membrenolytic p(NIPAM)55-b-p(His)n polymers are investigated for their use as a stimuli responsive drug carrier for tumor targeting. Highly uniform self-assembled micelles (∼55 nm) fabricated by p(NIPAM)55-b-p(His)n polymers display sharp thermal and pH responses in aqueous media. An anticancer drug, doxorubicin (Dox), is effectively encapsulated in the micelles and the controlled Dox release is investigated in different temperature and pH conditions. Antitumor effect of the released Dox is also assessed using the HepG2 human hepatocellular carcinoma cell lines. Dox molecules released from the [p(NIPAM)55-b-p(His)n] micelles remain biologically active and have stimuli responsive capability to kill cancer cells. The self-assembling ability of these hybrid materials into uniform micelles and their efficiency to encapsulate Dox makes them a promising drug carrier to cancer cells. The new chimeric materials thus display tunable properties that can make them useful for a molecular switching device and controlled drug delivery applications needing responses to temperature and pH for the improvement of cancer chemotherapy.

HS-1793, a recently developed resveratrol analogue protects rat heart against hypoxia/reoxygenation injury via attenuating mitochondrial damage.

Resveratrol is known to exert a cardioprotective effect against hypoxia/reoxygenation (H/R) injury. HS-1793 is a novel, more stable resveratrol analog, but its cardioprotective effects were unknown. The present study aimed to test the cardioprotective effect of HS-1793 against H/R injury and investigate the role of mitochondria in Sprague Dawley rat heart damage using an ex vivo Langendorff system. HS-1793 ameliorated H/R-induced mitochondrial dysfunction by reducing mitochondrial reactive oxygen species production, improving mitochondrial oxygen consumption and suppressing mitochondrial calcium (Ca(2+)) overload during reperfusion. Moreover, HS-1793-treated rat heart showed reduced infarct size. Our data suggest that HS-1793 can protect cardiac against mitochondrial damage following H/R, thereby suppressing injury.

Efficient and Stable Perovskite Solar Cells with a High Open-Circuit Voltage Over 1.2 V Achieved by a Dual-Side Passivation Layer.

Suppressing nonradiative recombination at the interface between the organometal halide perovskite (PVK) and the charge-transport layer (CTL) is crucial for improving the efficiency and stability of PVK-based solar cells (PSCs). Here, a new bathocuproine (BCP)-based nonconjugated polyelectrolyte (poly-BCP) is synthesized and this is introduced as a "dual-side passivation layer" between the tin oxide (SnO2 ) CTL and the PVK absorber. Poly-BCP significantly suppresses both bulk and interfacial nonradiative recombination by passivating oxygen-vacancy defects from the SnO2 side and simultaneously scavenges ionic defects from the other (PVK) side. Therefore, PSCs with poly-BCP exhibits a high power conversion efficiency (PCE) of 24.4% and a high open-circuit voltage of 1.21 V with a reduced voltage loss (PVK bandgap of 1.56 eV). The non-encapsulated PSCs also show excellent long-term stability by retaining 93% of the initial PCE after 700 h under continuous 1-sun irradiation in nitrogen atmosphere conditions.

Fabrication of nanotubules and microspheres from the self-assembly of amphiphilic monochain stearic acid derivatives.

A series of amphiphilic monochain derivatives of stearic acid, CH(3)(CH(2))(16)CONH(CH(2))(n)NH(2) (n = 2, 3, 4, 6), CH(3)(CH(2))(16)CONH(CH(2))(2)S(2)(CH(2))(2)NH(2), and [CH(3)(CH(2))(16)CONH](2)(CH(2))(2), are synthesized, and their self-assembly behaviors have been investigated in 1,2-dichloroethane (DCE). In addition to the concentration of the compound in DCE, the number of methylene units in hydrophilic segments play a crucial role in determining the final morphology of self-assembling structures from nanotubules with 20 nm inner diameter to microspheres with an average diameter of 20 µm. The external texture of the microsphere is also influenced by the number of methylene units in the hydrophilic segment. The microspheres formed by highly ordered aggregation of nanobelts show high thermal stability. The particular processes and causations have been expatiated.

Hyperbranched polyglycidol assisted green synthetic protocols for the preparation of multifunctional metal nanoparticles.

Biocompatible hyperbranched polyglycidol (HBP) has been demonstrated to be an effective reducing and stabilizing agent for the synthesis of highly water-soluble monometallic (Au, Ag, Pt, Pd, and Ru) and bimetallic (Au/Pt, Au/Pd, and Au/Ru) nanoparticles (NPs), which provides a general and green protocol to fabricate metal NPs. The HBP-assisted reduction of metal ions follows an analogous polyol process. The reduction reaction rate increases sharply by increasing the temperature and the molecular weight of HBP. The size of NPs is controllable simply by changing the concentration of the metal precursor. High molecular weight HBP is favorable for the formation of NPs with uniform size and improved stability. By utilizing hydroxyl groups in the HBP-passivation layer of Au NPs, TiO(2)/Au, GeO(2)/Au, and SiO(2)/Au nanohybrids are also fabricated via sol-gel processes, which sets a typical example for the creation of versatile metal NPs/inorganic oxide hybrids based on the as-prepared multifunctional NPs.

A newly synthesized, potent tyrosinase inhibitor: 5-(6-hydroxy-2-naphthyl)-1,2,3-benzenetriol.

In searching for new agents with a depigmenting effect, we synthesized a derivative of resveratrol, 5-(6-hydroxy-2-naphthyl)-1,2,3-benzenetriol (5HNB) with a potent tyrosinase inhibitory activity. 5HNB inhibited mushroom tyrosinase with an IC(50) value of 2.95 microM, which is more potent than the well-known anti-tyrosinase activity of kojic acid (IC(50)=38.24). The results of the enzymatic inhibition kinetics by Lineweaver-Burk analysis indicated 5HNB inhibits tyrosinase non-competitively when L-tyrosine was used as the substrate. Based on the strong inhibitory action of 5HNB, it is expected that 5HNB can suppress melanin production in which tyrosinase plays the essential role. Our expectation was confirmed by the experimentations with B16 melanoma cells in which 5HNB inhibited melanin production. We propose that 5HNB might have skin-whitening effects as well as therapeutic potential for treating skin pigmentation disorders.

Enhanced open circuit voltage by hydrophilic ionic liquids as buffer layer in conjugated polymer-nanoporous titania hybrid solar cells.

We demonstrate the fabrication of a nanoporous titania (NP-TiO(2)) network structure by using a polystylene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymer template and modifying the surface of NP-TiO(2) with ionic liquids (ILs), bmim-BF(4) and benmim-Cl. The effect of the molecular weight of PS-b-P4VP on the morphology of the NP-TiO(2) and IL-modified NP-TiO(2) are characterized by scanning electron microscopy and contact angle measurements. Subsequently, hybrid solar cells are fabricated using MEH-PPV and NP-TiO(2), and the effect of IL layers and IL concentrations on device performances are evaluated under AM 1.5 G illumination. The devices containing bmim-BF(4) and benmim-Cl show drastically enhanced open circuit voltages (V(oc)) of 1.05 V and 0.91 V, respectively, while the reference device without an IL layer exhibits a V(oc) of 0.60 V. Significantly improved V(oc) can be attributed to the change in interfacial energy levels by formation of ionic double layers at the TiO(2)/IL and at the IL/MEH-PPV interfaces. We also observed the trend that short circuit current decreased and V(oc) increased with increasing IL concentration, which is ascribed to interruption of charge transfer from MEH-PPV to TiO(2) and the change in interfacial energy level by shifting the vacuum level, respectively.

Efficacy on anaplastic thyroid carcinoma of valproic acid alone or in combination with doxorubicin, a synthetic chenodeoxycholic acid derivative, or lactacystin.

The present study investigated the mechanism underlying the antitumor activity of the histone deacetylases inhibitor valproic acid (VPA), alone and in combination with doxorubicin, a synthetic chenodeoxycholic acid derivative (HS-1200), or the proteasome inhibitor lactacystin on cultured anaplastic thyroid carcinoma KAT-18 cells. Cell viability was evaluated by trypan-blue exclusion. Western blotting determined caspase and histone deacetylase activities and expression of poly(ADP)-ribose polymerase. Induction of apoptosis was identified by Hoechst staining, DNA electrophoresis, DNA hypoploidy and cell cycle phase analysis, and measurement of mitochondrial membrane potential. Subcellular translocation of apoptosis inducing factor and caspase-activated DNase after treatment was determined by confocal microscopy following immunofluorescent staining. VPA treatment increased apoptotic death of KAT-18 cells. VPA treatment was also associated with degradation of procaspase-3, procaspase-7, and poly(ADP)-ribose polymerase; induction of histone hyperacetylation; condensation of peripheral chromatin; decreased mitochondrial membrane potential and DNA content; and decreased translocation of apoptosis inducing factor and caspase-activated DNase. VPA in combination with doxorubicin, HS-1200, or lactacystin, applied at the highest concentrations that did not induce KAT-18 cell death, efficiently induced apoptosis in KAT-18 cells. The results suggest VPA combination therapy may represent an alternative therapeutic strategy for anaplastic thyroid carcinoma.

Counterion effects on fluorescence energy transfer in conjugated polyelectrolyte-based DNA detection.

Cationic poly[9,9'-bis[6''-(N,N,N-trimethylammonium)hexyl]fluorene-co-alt-phenylene]s with five different counterions (CIs) were synthesized and studied as fluorescence resonance energy transfer (FRET) donors (D) to dye-labeled DNA (FRET acceptor, A). The polymers with different CIs show the same pi-conjugated electronic structure with similar absorption (lambda(abs) = approximately 380 nm) and photoluminescence (lambda(PL) = approximately 420 nm) emission spectra in water. The CIs accompanying the polymer chain are expected to affect the D/A complexation and modify the D-A intermolecular separation by acting as a spacer. Polymers with different CIs function differently as FRET excitation donors to fluorescein (Fl)-labeled single-stranded DNA (ssDNA-Fl). The FRET-induced Fl emission was enhanced significantly by the larger CI-exchanged polymers. The polymers with the CIs of tetrakis(1-imidazolyl)borate (FPQ-IB) and tetraphenylborate (FPQ-PB) showed a 2-4-fold enhancement in the FRET-induced signal compared with the polymer with bromide (FPQ-BR). The delayed FRET signal saturation and low association constants (K(a)) with ssDNA-Fl (3.53 x 10(6) M(-1) for FPQ-BR and 1.80 x 10(6) M(-1) for FPQ-PB) were measured for the polymers with larger CIs. The delayed acceptor saturation strengthens the antenna effect and reduces self-quenching of Fl by increasing the polymer concentration near Fl. The weak polymer/ssDNA-Fl association reduces the amount of energy-wasting charge transfer by increasing D-A intermolecular separation. The combined effects lead to increase the overall FRET-induced signal.

Inhibitory effects of 6-(3-hydroxyphenyl)-2-naphthol on tyrosinase activity and melanin synthesis.

As a part of an ongoing project searching for new skin-lightening agents, the inhibitory property of 6-(3-Hydroxyphenyl)-2-naphthol (HPN) on melanogenesis was investigated. The inhibitory action of HPN (IC(50)=15.2 muM) on mushroom tyrosinase was revealed. To further explore the action of HPN on melanogenesis, the inhibition of tyrosinase and melanin levels were measured in B16 melanoma cells (B16 cells). Results show that HPN inhibited tyrosinase activity and reduced melanin in B16 cells. Therefore, our data indicate HPN as a new candidate for depigmentation reagents.

Synthesis and application of amine-containing conjugated small molecules for the automatic formation of an electron transporting layer via spontaneous phase separation from the bulk-heterojunction layer.

Carbazole-based conjugated small molecule electrolytes (CSEs) containing different numbers of amine groups were synthesized and applied to bulk-heterojunction (BHJ) organic solar cells for the formation of a spontaneous self-assembled electron transporting layer (ETL). The active layer was spin-coated with a mixture solution containing the BHJ materials and a small amount of CSE, and a thin layer of CSE was formed underneath the active layer (CSE/BHJ bi-layer) via spontaneous phase separation, which is confirmed by the depth profile of the time of flight secondary ion mass spectroscopy (ToF-SIMS) spectrum. The amino groups in the CSEs form hydrogen-bonds with the surface of indium tin oxide (ITO), which acts as an ETL in BHJ solar cells. Moreover, the formed CSE layer is capable of changing the effective work function (WF) of ITO. An increasing number of amino groups in the CSEs (from Cz1N to Cz3N) provides more reduction of the effective WF of ITO, which results in a lower internal resistance and a higher power conversion efficiency (PCE). Furthermore, the enhanced hydrogen bonding between the amines and ITO with an increased number of amine groups has been studied by XPS. This result suggests that one-step processing provides a reduction of the manufacturing cost, which can provide an attractive design concept for ETL fabrication.

A novel chenodeoxycholic derivative HS-1200 enhances radiation-induced apoptosis in MCF-7 cells.

HS-1200, a synthetic chenodeoxycholic acid derivative, has cytotoxic activity in various human cancer cells. The present study was undertaken to examine whether HS-1200 sensitizes radiation-induced apoptosis in MCF-7 human breast carcinoma cells. Clonogenic assay elucidated that the combination treatment with HS-1200 and radiation induced more cytotoxic effects than the radiation treatment alone. Nuclear staining, DNA electrophoresis and Western blot analysis for poly(ADP-ribose) polymerase revealed that the increased cytotoxic effect by the combination treatment resulted from the augmentation of apoptosis. There was an increase in the expression level of Bax and its translocation onto the mitochondria, a reduction in the mitochondrial membrane potential in the earlier time-points, and the release of cytochrome c into the cytosol increased in the MCF-7 cells treated with radiation and HS-1200 compared to the cells treated only with radiation. Therefore, the synthetic bile acid derivative, HS-1200, could have the therapeutic potential as a radiosensitizer in MCF-7 cells.