Novel polythiophene derivatives functionalized withconjugated side-chain pendants comprisingtriphenylamine/carbazole moieties for photovoltaic cellapplications†

We synthesized a series of polythiophenes (PTs) featuring 2-ethylhexyl-substituted terthiophene (T) orquaterthiophene (BT) as the conjugated unit in the polymer backbone with pendant conjugated tertbutyl-substituted triphenylamine (tTPA)- or carbazole (tCz)-containing moieties as side chains, namelyPTtTPA, PBTtTPA, PTtCz and PBTtCz. Incorporating T and BT moieties into the polymer backbone andattaching tTPA or tCz units promoted efficient conjugation within the extended conjugated frameworksof the polymers, resulting in lower band-gap energies and red-shifting of the maximal UV-Visabsorption wavelength. The higher electron-donating ability of tTPA resulted in broader absorptionbands and lower band-gap energies of PTtTPA and PBTtTPA as compared with PTtCz and PBTtCz.Incorporation of the T and BT moieties into the polymer backbone enhanced the compatibility of PTand the fullerene derivative by reducing the side-chain density of PT, thus providing sufficient freevolume for efficient incorporation of [6,6]phenyl-C61-butyric acid methyl ester (PC61BM) into thepolymer chains. Polymer solar cells (PSCs) were fabricated by spin-coating a blend of each PT with thefullerene derivative (PC61BM) as a composite film-type photoactive layer; PBTtTPA/PC61BM-based PSCsshowed superior photovoltaic (PV) performance to PTtTPA/PC61BM-based PSCs in terms of conjugationand absorption band broadness. However, PBTtCz/PC61BM-based PSCs showed inferior PV performanceto PTtCz/PC61BM-based PSCs. The lower HOMO level led to a higher open-circuit voltage (Voc; 0.74 V)and larger photo-energy conversion efficiency (h; 2.77%) of PTtCz/PC61BM-based PSCs

Polythiophenes comprising conjugated pendantstoward long-term air-stable inverted polymer solar cellswith high open circuit voltages

A series of polythiophenes (PTs) functionalized with bulky conjugated side chains comprising tert-butylsubstituted carbazole (tCz) as an electron donor pendant and bisbenzothiazolylvinyl (DBT) as anelectron acceptor pendant were synthesized via Stille copolymerization for polymer solar cell (PSC)applications. We use the descriptors PTtCz, PT(tCz)0.9(DBT)0.1, PT(tCz)0.64(DBT)0.36, PT(tCz)0.45(DBT)0.55,and PTDBT to identify each of these conjugated polymers, with the names denoting the compositionsof the bulky pendants. The tunable energy levels of the PTs were accomplished by incorporating bothtCz as a donor pendant and DBT as an acceptor pendant, while retaining the low-lying HOMO levels( 5.26 to 5.39 eV). Furthermore, lower bandgaps were observed for the DBT-derived PTs because ofstronger donor–p–acceptor characteristics and more efficient intramolecular charge transfer.Conventional PSCs were fabricated by spin-coating the blend of each PT and the fullerene derivative(PC71BM). The conventional PSC devices exhibited high open circuit voltages (Voc) of around 0.79–0.91 V. The power conversion efficiency (PCE) of the PSCs based on PTtCz : PC71BM (w/w ¼ 1 : 2.5)reached 2.48% with a Voc of 0.91 V, short circuit current (Jsc) of 6.58 (mA cm 2) and fill factor (FF) of41% under the illumination of AM1.5, 100 mW cm 2. Furthermore, a PTtCz/PC71BM-based inverted PSCwith ZnOx and MoO3 as an electron extraction layer and a hole extraction layer respectively was capableof retaining ca. 80% of its original efficiency after storage under ambient conditions (withoutencapsulation) for 1032 h, according to the ISOS-D-1 shelf protocol. The highly durable inverted PSCaccompanied by a large Voc value was achieved for the PT-type polymers

DC-SIGN (CD209) Promoter −336 A/G Polymorphism Is Associated with Dengue Hemorrhagic Fever and Correlated to DC-SIGN Expression and Immune Augmentation

Dengue fever (DF) is an arthropod-borne disease that is prevalent in tropical and subtropical regions of the world. DC-SIGN [dendritic cell-specific intercellular adhesion molecule 3 (ICAM-3)-grabbing non-integrin] is a major receptor for dengue infection. DC-SIGN, also called CD209, expresses on dendritic cells (DCs) that bind to ICAM-3, which is expressed on T cells to facilitate the initial interaction between DCs and T cells. Variations in the CD209 promoter (−336 A/G; rs4804803) genotype are involved in the pathogenesis of human infectious diseases. Here we found that patients with dengue hemorrhagic fever (DHF) had a higher frequency of the AG or GG genotype of rs4804803 than DF or controls. Functional studies determined that monocyte-derived DCs (MDDCs) from individuals with AG genotype had significantly higher cell surface DC-SIGN expression, associated with higher TNFα, IL-12p40, and IP-10 production, but lower viral replication than those with AA genotype. An increase in DEN-2 replication in MDDCs was observed following the addition of anti-IP-10 neutralizing antibody. These findings highlight the fact that the rs4804803 SNP in the CD209 promoter is associated with DHF and correlated to DC-SIGN expression and immune augmentation

Bacterial Peptidoglycan Triggers Candida albicans Hyphal Growth by Directly Activating the Adenylyl Cyclase Cyr1p

SummaryHuman serum potently induces hyphal development of the polymorphic fungal pathogen Candida albicans, a phenotype that contributes critically to infections. The fungal adenylyl cyclase Cyr1p is a key component of the cAMP/PKA-signaling pathway that controls diverse infection-related traits, including hyphal morphogenesis. However, identity of the serum hyphal inducer(s) and its fungal sensor remain unknown. Our initial analyses of active serum fractions revealed signs of bacterial peptidoglycan (PGN)-like molecules. Here, we show that several purified and synthetic muramyl dipeptides (MDPs), subunits of PGN, can strongly promote C. albicans hyphal growth. Analogous to PGN recognition by the mammalian sensors Nod1 and Nod2 through their leucine-rich-repeat (LRR) domain, we show that MDPs activate Cyr1p by directly binding to its LRR domain. Given the abundance of PGN in the intestine, a natural habitat and invasion site for C. albicans, our findings have important implications for the mechanisms of infection by this pathogen

Acute effect of electroacupuncture at the Zusanli acupoints on decreasing insulin resistance as shown by lowering plasma free fatty acid levels in steroid-background male rats

<p>Abstract</p> <p>Background</p> <p>Insulin sensitivity has been enhanced by electroacupuncture (EA) in rats, but the EA phenomenon in an insulin resistant state is still unclear. This study reports the use of a large dose of prednisolone to evaluate the effects of EA in a state of insulin resistance.</p> <p>Methods</p> <p>The plasma levels of free fatty acids (FFAs) were estimated in steroid-background rats (SBRs) and compared with those in healthy rats treated with normal saline. In addition, plasma glucose and endogenous insulin levels were assayed to calculate the homeostasis model assessment (HOMA) index. Intravenous glucose tolerance test (IVGTT) was carried out to compare glucose tolerance. The SBRs were randomly divided into EA-treatment and non-EA treatment groups and 15-Hz EA was applied to the bilateral Zusanli acupoints to investigate its effects on insulin resistance. In addition to an insulin challenge test (ICT) and IVGTT, the plasma levels of FFAs were measured and western blot was performed to help determine the effects of EA on the insulin resistant state.</p> <p>Results</p> <p>The plasma levels of FFAs increased markedly in SBRs, the HOMA index was markedly higher, and glucose tolerance was impaired. EA improved glucose tolerance and insulin sensitivity by decreasing the plasma levels of FFAs. Further, the insulin signaling proteins (IRS1) and glucose transporter isoform protein (GLUT4) in skeletal muscle inhibited by prednisolone recovered after EA.</p> <p>Conclusion</p> <p>Insulin resistance was successfully induced by a large dose of prednisolone in male rats. This insulin resistance can be improved by 15 Hz EA at the bilateral Zusanli acupoints, as shown by decreased plasma levels of FFAs.</p

BIPV-Powered Smart Windows Utilizing Photovoltaic and Electrochromic Devices

A BIPV-powered smart window comprising a building-integrated photovoltaic (BIPV) panel and an all-solid-state electrochromic (EC) stack is proposed. In the proposed device, the output voltage of the BIPV panel varies in accordance with the intensity of the incident light and is modulated in such a way as to generate the EC stack voltage required to maintain the indoor illuminance within a specified range. Two different EC stacks are fabricated and characterized, namely one stack comprising ITO/WO3/Ta2O5/ITO and one stack comprising ITO/WO3/lithium-polymer electrolyte/ITO. It is shown that of the two stacks, the ITO/WO3/lithium-polymer electrolyte/ITO stack has a larger absorptance (i.e., approximately 99% at a driving voltage of 3.5 V). The experimental results show that the smart window incorporating an ITO/WO3/lithium-polymer electrolyte/ITO stack with an electrolyte thickness of 1.0 μm provides an indoor illuminance range of 750–1,500 Lux under typical summertime conditions in Taiwan

Microstructure-Stabilized Blue Phase Liquid Crystals

We show that micron-scale two-dimensional (2D) honeycomb microwells can significantly improve the stability of blue phase liquid crystals (BPLCs). Polymeric microwells made by direct laser writing improve various features of the blue phase (BP) including a dramatic extension of stable temperature range and a large increase both in reflectivity and thermal stability of the reflective peak wavelength. These results are mainly attributed to the omni-directional anchoring of the isotropically oriented BP molecules at the polymer walls of the hexagonal microwells and at the top and bottom substrates. This leads to an omni-directional stabilization of the entire BPLC system. This study not only provides a novel insight into the mechanism for the BP formation in the 2D microwell but also points to an improved route to stabilize BP using 2D microwell arrays.Comment: 16 pages, 5 figure

Orderly arranged NLO materials on exfoliated layeredtemplates based on dendrons with alternating moietiesat the periphery†

Nonlinear optical dendrons with alternating terminal groups of the stearyl group (C18) and chromophorewere prepared through a convergent approach. These chromophore-containing dendrons were used asthe intercalating agents for montmorillonite via an ion-exchange process. An orderly exfoliatedmorphology is obtained by mixing the dendritic structure intercalated layered silicates with a polyimide.As a result, optical nonlinearity, i.e. the Pockels effect was observed for these nanocomposites withoutresorting to the poling process. EO coefficients of 9–22 pm V 1 were achieved despite that relativelylow NLO densities were present in the nanocomposites, particularly for the samples comprising thedendrons with alternating moieties. In addition, the hedging effects of the stearyl group on the selfalignmentbehavior, electro-optical (EO) coefficient and temporal stability of the dendron-intercalatedmontmorillonite/polyimide nanocomposites were also investigated

(31) P and (1) H MRS of DB-1 melanoma xenografts: lonidamine selectively decreases tumor intracellular pH and energy status and sensitizes tumors to melphalan.

In vivo (31) P MRS demonstrates that human melanoma xenografts in immunosuppressed mice treated with lonidamine (LND, 100 mg/kg intraperitoneally) exhibit a decrease in intracellular pH (pH(i) ) from 6.90 ± 0.05 to 6.33 ± 0.10 (p \u3c 0.001), a slight decrease in extracellular pH (pH(e) ) from 7.00 ± 0.04 to 6.80 ± 0.07 (p \u3e 0.05) and a monotonic decline in bioenergetics (nucleoside triphosphate/inorganic phosphate) of 66.8 ± 5.7% (p \u3c 0.001) relative to the baseline level. Both bioenergetics and pH(i) decreases were sustained for at least 3 h following LND treatment. Liver exhibited a transient intracellular acidification by 0.2 ± 0.1 pH units (p \u3e 0.05) at 20 min post-LND, with no significant change in pH(e) and a small transient decrease in bioenergetics (32.9 ± 10.6%, p \u3e 0.05) at 40 min post-LND. No changes in pH(i) or adenosine triphosphate/inorganic phosphate were detected in the brain (pH(i) , bioenergetics; p \u3e 0.1) or skeletal muscle (pH(i) , pH(e) , bioenergetics; p \u3e 0.1) for at least 120 min post-LND. Steady-state tumor lactate monitored by (1) H MRS with a selective multiquantum pulse sequence with Hadamard localization increased approximately three-fold (p = 0.009). Treatment with LND increased the systemic melanoma response to melphalan (LPAM; 7.5 mg/kg intravenously), producing a growth delay of 19.9 ± 2.0 days (tumor doubling time, 6.15 ± 0.31 days; log(10) cell kill, 0.975 ± 0.110; cell kill, 89.4 ± 2.2%) compared with LND alone of 1.1 ± 0.1 days and LPAM alone of 4.0 ± 0.0 days. The study demonstrates that the effects of LND on tumor pH(i) and bioenergetics may sensitize melanoma to pH-dependent therapeutics, such as chemotherapy with alkylating agents or hyperthermia

Anti-AIDS Agents 69. Moronic Acid and Other Triterpene Derivatives as Novel Potent Anti-HIV Agents

In a continuing structure-activity relationship study of potent anti-HIV agents, seven new triterpene derivatives were designed, synthesized, and evaluated for in vitro antiviral activity. Among them, moronic acid derivatives 19, 20 and 21 showed significant activity in HIV-1 infected H9 lymphocytes. Compounds 19 and 20 were also evaluated against HIV-1 NL4−3 and drug resistant strains in the MT-4 cell line. Compounds 19 and 20 showed better antiviral profiles than the betulinic acid analog 8 (PA-457), which has successfully completed a Phase IIa clinical trial. Compound 20 showed potent anti-HIV activity with EC50 values of 0.0085 μM against NL4−3, 0.021 μM against PI-R (a multiple protease inhibitor resistant strain), and 0.13 μM against FHR-2 (an HIV strain resistant to 8), respectively. The promising compound 20 has become a new lead for modification, and further development of 20-related compounds as clinical trial candidates is warranted