Nitric oxide turn-on fluorescent probe based on deamination of aromatic primary monoamines

The stable, water-soluble, and nonfluorescent FA-OMe can sense nitric oxide (NO) and form the intensely fluorescent product dA-FA-OMe via reductive deamination of the aromatic primary amine. The reaction is accompanied by a notable increase of the fluorescent quantum yield from 1.5 to 88.8%. The deamination mechanism of FA-OMe with NO was proposed in this study. The turn-on fluorescence signals were performed by suppression of photoinduced electron transfer (PeT), which was demonstrated by density functional theory (DFT) calculations of the components forming FA-OMe and dA-FA-OMe. Furthermore, FA-OMe showed water solubility and good stability at physiological pHs. Moreover, the selectivity study indicated that FA-OMe had high specificity for NO over other reactive oxygen/nitrogen species. In an endogenously generated NO detection study, increasing the incubation time of FA-OMe with lipopolysaccharide (LPS) pretreated Raw 264.7 murine macrophages could cause an enhanced fluorescence intensity image. In addition, a diffusion/localization cell imaging study showed that FA-OMe could be trapped in Raw 264.7 cells. These cell imaging results demonstrated that FA-OMe could be used as a turn-on fluorescent sensor for the detection of endogenously generated NO.     

Using “Threading Followed by Shrinking” to Synthesize Highly Stable Dialkylammonium‐Ion‐Based Rotaxanes

Herein, we report a “threading followed by shrinking” approach for the synthesis of rotaxanes by using an “oxygen‐deficient” macrocycle that contained two arylmethyl sulfone units and the dumbbell‐shaped salt bis(3,5‐dimethylbenzyl)ammonium tetrakis(3,5‐trifluoromethylphenyl)borate as the host and guest components, respectively. The extrusion of SO₂ from both of the arylmethyl sulfone units of the macrocyclic component in the corresponding [2]pseudorotaxane resulted in a [2]rotaxane that was sufficiently stable to maintain its molecular integrity in CD₃SOCD₃ at 393 K for at least 5 h.     

Euphorbiane: A Novel Triterpenoid with an Unprecedented Skeleton from Euphorbia tirucalli

Euphorbiane ( 1 ), a novel triterpenoid exhibiting a unique skeleton, together with seven known compounds were isolated from the 95% EtOH extract of the fresh stems of Euphorbia tirucalli. The structure of 1 and relative stereochemistry were elucidated by extensive NMR and a single‐crystal X‐ray crystallographic analysis.     

TiO2 Thin Film with Varied Porous Structure Applied on the Degradation of Methylene Blue

In this study, porous TiO₂ thin films were prepared by the sol‐gel method employing polyethylene glycol 1000 (PEG 1000) as an organic template. Pore sizes were adjusted by varying the concentration of PEG 1000. The optimal PEG concentration range required to form TiO₂ films with a regular porous structure was investigated and was found to be 0.01–0.015 M. As the PEG 1000 concentration increased, the surface of these films became rougher because of larger pores. Degradation of methylene blue (MB) under UV irradiation was used to determine the photocatalytic activity of the films. In addition, the effect of the pH value of the MB solution on the films was evaluated by controlling its pH value at 5, 7, and 9. The results showed that the photocatalytic activity was correlated to the pore size and pore density of the thin films. TiO2 thin films possessing pore sizes in the diameter range of 35–85 nm exhibited the best conversion of 98% after 8 h of UV irradiation when the pH value was 7.     

Effects of the acceptor conjugation length and composition on the electrical memory characteristics of random copolyimides

Resistive‐switching memories based on copolyimides (coPIs), PI‐NTCDIX and PI‐BTCDIX , with different compositions of 4,4′‐diamino‐4″‐methyltriphenylamine ( AMTPA ), 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, and N,N′‐bis‐(4‐aminophenyl)‐1,8:4,5‐naphthalenetetracarboxydiimide ( NTCDI ) or N,N′‐bis‐(4‐aminophenyl)‐1,2:4,5‐benzenetetracarboxydiimide ( BTCDI ) have been developed. By varying the feed ratio of monomers, PI‐NTCDIX and PI‐BTCDIX showed tunable optical and electronic properties through the charge transfer (CT) between AMTPA and NTCDI or BTCDI . The memory devices based on PI‐NTCDIX exhibited the tunable electrical bistability from the volatile dynamic random access memory to nonvolatile write once read many memory characteristics as the NTCDI composition increased. The OFF/ON electrical switching transition was mainly attributed to the CT mechanism for the charge separated high conductance, based on the analysis of model compounds and density functional theory calculation. Also, the volatility of the memory device depended on the stability of CT complex. The long conjugation and high electron affinity of the NTCDI moiety stabilized the radical anion generated in the CT complex and prevented the recombination of segregated radical species even through applying the high positive or negative voltage. On the other hand, the memory devices based on PI‐BTCDIX showed a rather unique behavior compared with those based on PI‐NTCDIX . At the low BTCDI composition, the device exhibited volatile memory property. However, no switching behavior was observed at the high BTCDI composition due to the low highest occupied molecular orbital energy level of BTCDI . Combining these results and our previous study on perylenebisimide ( PBI ), we concluded that memory characteristics could be tailored by changing the conjugation length ( PBI > NTCDI > BTCDI ) and the acceptor composition in random coPIs. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

A convenient and sensitive method for haloacetic acid analysis in tap water by on‐line field‐amplified sample‐stacking CE–ESI‐MS

In this study, we propose a simple strategy based on flow injection and field‐amplified sample‐stacking CE–ESI‐MS/MS to analyze haloacetic acids (HAAs) in tap water. Tap water was passed through a desalination cartridge before field‐amplified sample‐stacking CE–ESI‐MS/MS analysis to reduce sample salinity. With this treatment, the signals of the HAAs increased 300‐ to 1400‐fold. The LODs for tap water analysis were in the range of 10 to 100 ng/L, except for the LOD of monochloroacetic acid (1 μg/L in selected‐ion monitoring mode detection). The proposed method is fast, convenient, and sensitive enough to perform on‐line analysis of five HAAs in the tap water of Taipei City. Four HAAs, including trichloroacetic acid, dichloroacetic acid, dibromoacetic acid, and monobromoacetic acid, were detected at concentrations of approximately 1.74, 1.15, 0.16, and 0.15 ppb, respectively.     

Detecting small lung tumors in mouse models by refractive-index microradiology

Refractive-index (phase-contrast) radiology was able to detect lung tumors less than 1 mm in live mice. Significant micromorphology differences were observed in the microradiographs between normal, inflamed, and lung cancer tissues. This was made possible by the high phase contrast and by the fast image taking that reduces the motion blur. The detection of cancer and inflammation areas by phase contrast microradiology and microtomography was validated by bioluminescence and histopathological analysis. The smallest tumor detected is less than 1 mm(3) with accuracy better than 1 × 10(-3) mm(3). This level of performance is currently suitable for animal studies, while further developments are required for clinical application.     

A Highly diastereoselective synthesis of (1R)-(+)-camphor-based chiral allenes and their asymmetric hydroboration-oxidation reactions

Synthesis of camphor derived chiral allenes and their hydroboration-oxidation reactions are described. Reaction of (1R)-(+)-camphor with alkynyllithium followed by the reduction of the resulted propargyl alcohol derivatives using AlH3 furnished chiral allenes 2a-g in excellent yields with high diastereoselectivity. Reduction of the propargyl alcohols with aluminum hydride proceeded through selective intermolecular anti-addition of hydride ion. The stereochemistry of the chiral allenes 2 was assigned based on lanthanide shift studies and chemical correlations. Diastereoselectivity was observed in the hydroboration-oxidation of 2 which produced a mixture of (E,R) and (E,S) stereoisomers in a ratio of 6:1 to 18:1.     

Transient resonance Raman and density functional theory investigation of the chlorine atom/carbon disulfide molecular complex involved in selective alkane photochlorination reactions

The structure and bonding of the chlorine atom/carbon disulfide (CS(2)/Cl) complex involved in selective photochlorination reactions with alkanes was directly probed using transient resonance Raman spectroscopy. The experimental Raman vibrational frequencies were compared to those computed from density functional theory calculations for probable structures of the CS(2)/Cl complex. Our results indicate that the S [double bond] C [double bond] S...Cl complex species is responsible for the approximately 370 nm transient absorption band observed after ultraviolet photolysis of CCl(4) in the presence of CS(2). We discuss the structure and properties of the S [double bond] C [double bond] S...Cl complex and compare them with those for the related benzene/Cl and pyridine/Cl complexes.