Synthesis and characterization of cross‐linkable ruthenium complex dye and its application on dye‐sensitized solar cells

A new crosslinkable light sensitizer, Ru(2,2′‐bipyridine‐4,4′‐bicarboxylic acid)(4,4′‐bis(11‐dodecenyl)‐2,2′‐bipyridine)(NCS)₂, denoted as Ru‐C for titanium oxide nanocrystalline‐based solar cells was synthesized with its crosslinking properties invesitigated by Fourier‐transform infrared and UV‐vis absorption spectroscopies. After crosslinking by itself or copolymerizing with methyacrylic acid, their sensitized solar cells with poly(methylacrylate)‐gelled electrolyte system not only attained more than 5% of power conversion efficiency at AM 1.5 illumination (100 mW/cm²), but also gave rise to long storage life. To the best our knowledge, this is the first crosslinkable dye ever applied to the DSSC in the literature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 366–372, 2010     

Phytoquinoids and Secoprezizaane‐Type Sesquiterpenes from Illicium arborescens

A phytochemical investigation of the MeOH extract of Illicium arborescens yielded the two new phytoquinoid epimers, 2,3‐didehydro‐5‐O‐methyl‐11‐epiillifunone E ( 1 ) and 2,3‐didehydro‐5‐O‐methylillifunone E ( 2 ), as well as five new sesquiterpene lactones (8,9‐secoprezizaane‐type sesquiterpenes). Two of them, i.e., 3 and 4 , were minwanensin‐type sesquiterpenes, the other two, i.e., 5 and 6 , had the anisatin‐type (or floridanolide type) skeleton, and the fifth, i.e., 7 , was a dunnianin‐type sesquiterpene. Their structures were established by analyses of 1D‐ and 2D‐NMR, HR‐MS, and chemical evidence. The in vitro cytotoxic activity of compounds 1 – 7 was tested against four human tumor cell lines, including HeLa (cervical epitheloid), WiDr (colon), Daoy (medulloblastoma), and Hep2 (liver carcinoma) human‐tumor cells.     

Synthesis and computational oxidation mechanism study of novel organosoluble aramids with high modulus by low‐temperature solution polycondensation

A series of highly organosoluble polyamides with high modulus having propeller‐shaped triarylamine were synthesized using aromatic diacid chlorides by low‐temperature solution polycondensation. The polyamide films had strong, tough, flexible, and amorphous properties. These polymers revealed electrochromic characteristics both in the visible range and near‐infrared (NIR) region, with a color change from pale yellowish at its neutral state to green and blue at its oxidized state at applied potentials ranging from 0.00 to 1.35 V. Cyclic voltammetry (CV) of the polymer films cast onto an indium tin oxide (ITO)‐coated glass substrate exhibited two reversible redox couples at potentials of 0.80–0.87 V and 1.19–1.25 V, respectively, vs. Ag/Ag⁺ in acetonitrile solution. From the combination of the experimental and computational study, we proposed an oxidation mechanism based on molecular orbital (MO) theory, which well explains the CV experimental result. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Anti-AIDS agents 83. Efficient microwave-assisted one-pot preparation of angular 2,2-dimethyl-2H-chromone containing compounds

A novel and efficient microwave-assisted one-pot reaction was developed to synthesize angular 2,2-dimethyl-2H-chromone-containing compounds, which is the first and key step in the synthesis of potent DCK and DCP anti-HIV agents. The newly developed microwave synthesis conditions dramatically shortened the reaction time from 2 days to 4 h with improved yields.     

Chemical composition and bioactivities of the marine alga Isochrysis galbana from Taiwan

The present study investigated the chemical composition of Isochrysis galbana Parke, a marine microalga which is widely used as a feedstock in aquaculture. From gas chromatography/mass spectrometric analysis the mono-sugar compositions of I. galbana were 2.1% fucose, 2.5% rhamnose, 2.7% arabinose, 8.5% xylose, 15.7% mannose, 32.7% galactose and 35.8% glucose. The polysaccharides of I. galbana were able to induce prointerleukin-1beta (pro-IL-1beta) protein expression within murine macrophages. Furthermore, five kinds of chlorophyll and one sterol were separated from the ethanolic extracts, including pheophorbide-a, ethyl pheophorbide-a, 10S-10-hydroxypheophytin-a, 10R-10-hydroxypheophytin-a, (132-R)-pheophytin-a, and brassicasterol. In addition, the major soluble components of the ethanol/n-hexane extract were 9-octadecenoic acid (E) (38.4%), hexadecanoic acid (23.3%), tetradecanoic acid (15.7%), and octadecanoic acid (7.2%), but only a few polyunsaturated fatty acids were found, such as 9,12,15-octadecatrienoic acid (1.9%), 9,12-octadecadienoic acid (Z,Z) (3.4%), and docosahexaenoic acid (0.2%). This is the first occasion that polysaccharides from I. galbana have been demonstrated to exert immunomodulatory properties by the induction of IL-1 within macrophages.     

Rapid determination of aristolochic acids I and II in herbal products and biological samples by ultra-high-pressure liquid chromatography-tandem mass spectrometry

Aristolochic acids (AAs) are a mixture of structural-related compounds, in which aristolochic acid I (AA I) and aristolochic acid II (AA II) are reported to be correlated with Aristolochic acid nephropathy (AAN). In this work, a rapid and sensitive ultra-high-pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed to determine AA I and AA II in herbal products and biological fluids. By using gradient elution with a mobile phase composed of a mixture of 10 mM ammonium formate buffer (pH 3.0) and acetonitrile, AAs could be determined within 10 min. Under optimum UHPLC-MS/MS conditions, the limit of detections was 0.14 and 0.26 ng mL⁻¹ for AA I and AA II, respectively. Run-to-run repeatability and intermediate precision of peak area for AA I and AA II were less than 5.74% relative standard deviation (RSD). Accuracy was tested by spiking 10, 100 and 1000 ng mL⁻¹ in rat serum and the recoveries were within 76.5-92.9%. Matrix effects were within 78.8-127.7%. The developed method was successfully applied to determine AA I and AA II in several herbal products and to investigate their pharmacokinetic behavior in female Wister rats. The result shows that the developed UHPLC-MS/MS method is efficient, sensitive, and accurate for the determination of AA I and AA II in herbal products and biological samples.     

Luminescence of Eu(DBM)3Phen-doped in azobenzene-containing copolymers—Effects of absorption overlapping of two components

Poly(N-isopropylacrylamide)-b-poly{6-[4-(4-methylphenyl-azo)phenoxy]hexylmethacrylate} (PNIPAM₃₂-b-PAzoMM₈) and poly(N-isopropylacrylamide)-b-poly{6-[methyl(4-nitrophenyldiazenyl)phenyl]aminohexylmethacrylate} (PNIPAM₃₂-b-PAzoNO₁₀) were prepared by reversible addition–fragmentation chain transfer (RAFT) radical polymerization. The optical properties of Eu(DBM)₃Phen (Eu, Europium; DBM, dibenzoylmethide; Phen, 1,10-phenanthroline)-doped azobenzene-containing copolymer vesicle solutions were studied by UV–vis and fluorescence spectroscopy. When the electronic transition bands of azobenzene and Eu(DBM)₃Phen overlapped at about 350 nm in PNIPAM₃₂-b-PAzoMM₈, the fluorescent emission intensity at 612 nm of Eu(DBM)₃Phen could be modulated by irradiation with UV and visible light. However, when the absorption of the azobenzene-moiety red-shifted to 477 nm in PNIPAM₃₂-b-PAzoNO₁₀, the luminescence intensity of Eu(DBM)₃Phen was not affected any longer. The difference between these two systems was possibly caused by the energy allocation in the luminescence process, which was discussed in detail.     

Novel oxazabicycles as a new class of photochromic colorants

A new photochromic colorant with an oxazabicyclic moiety has been synthesized by an efficient method. It turns pale red upon UV irradiation and undergoes reverse reaction while being heated. This work may open an exciting new avenue for future development of the photochromic dyes with novel molecular structures.     

Further structure–activity relationships study of substituted dithiolethiones as glutathione-inducing neuroprotective agents

Background

Parkinson’s disease is a neurodegenerative disorder associated with oxidative stress and glutathione depletion. The induction of cellular glutathione levels by exogenous molecules is a promising neuroprotective approach to limit the oxidative damage that characterizes Parkinson’s disease pathophysiology. Dithiolethiones, a class of sulfur-containing heterocyclic molecules, are known to increase cellular levels of glutathione; however, limited information is available regarding the influence of dithiolethione structure on activity. Herein, we report the design, synthesis, and pharmacological evaluation of a further series of dithiolethiones in the SH-SY5Y neuroblastoma cell line.

Results

Our structure–activity relationships data show that dithiolethione electronic properties, given as Hammett σ_p constants, influence glutathione induction activity and compound toxicity. The most active glutathione inducer identified, 6a, dose-dependently protected cells from 6-hydroxydopamine toxicity. Furthermore, the protective effects of 6a were abrogated by the inhibitor of glutathione synthesis, buthionine sulfoximine, confirming the importance of glutathione in the protective activities of 6a.

Conclusions

The results of this study further delineate the relationship between dithiolethione chemical structure and glutathione induction. The neuroprotective properties of analog 6a suggest a role for dithiolethiones as potential antiparkinsonian agents.