RNA Aptamers That Reversibly Bind Photoresponsive Azobenzene‐Containing Peptides

Modulation of biological networks assembled by diverse interactions among biologically active molecules has provided a platform for innovative biotechnologies. Here, we report RNA aptamers that bind to a photoresponsive peptide (KRAzR; Lys‐Arg‐azobenzene‐Arg) containing azobenzene chromophore, which can change its structure by photoirradiation. Aptamers were identified after 10 cycles of an in vitro selection procedure starting with a DNA library containing a 70 nt random region. Surface plasmon resonance (SPR) analysis demonstrated that interactions between aptamers and KRAzR were fully controlled by appropriate photoirradiation to the SPR sensor chip. Upon irradiation of 360 nm on the KRAzR‐immobilized surface, the binding of each aptamer to the surface was significantly decreased. Subsequent photoirradiation of the same surface with 430 nm restored the aptamer binding to the surface. We also observed that direct photoirradiation of the aptamer–peptide complex on a gold surface actively promoted dissociation of the complex. Furthermore, a doped reselection method was applied to acquire structural and sequence information of aptamer 66. From a data analysis of the conserved region and the mutation frequency, we were able to select a plausible secondary structure among three candidates predicted by computational folding simulation.     

An MRA study of vascular stenosis in a pig model using CH3-DTPA-Gd (NMS60) and Gd-DTPA

PURPOSE: This study used an experimental arterial stenosis model in pigs to evaluate the utility of a new medium-weight MRI contrast agent, NMS60 (a synthetic oligomeric Gd complex containing three Gd(3+) atoms, molecular weight of 2158 Da) compared to Gd-DTPA for contrast-enhanced MRA. MATERIALS AND METHODS: We used six male white hybrid pigs. Under anesthesia, one femoral artery was exposed and an inflatable cuff placed around it. The cuff was tightened around the vessel until 80-90% stenosis was achieved using digital subtraction angiography as a guide. Animals were then immediately transferred to the MRI scanner and images acquired pre- and postcontrast injection (0.1 or 0.2 mmol Gd/kg Gd-DTPA or NMS60, as a rapid bolus) using high-resolution and dynamic MRA. RESULTS: The dynamic MRA scans acquired during contrast bolus injection clearly showed the stenosed femoral artery as a segment of close to zero enhancement during the arterial phase of the bolus transit, while on the high-resolution scans the stenosis was difficult to detect due to venous signal contamination. The signal-to-noise at peak enhancement on the dynamic scans was significantly greater with 0.1 mmol Gd/kg NMS60 compared to 0.1 mmol Gd/kg Gd-DTPA (14.6 vs. 9.9, P < .05) and not significantly greater than 0.2 mmol Gd/kg (14.6 vs. 12.8). DISCUSSION AND CONCLUSION: This new medium-weight contrast agent demonstrated significantly greater enhancement than Gd-DTPA and may be valuable to aid detection of vascular stenosis in humans.     

强碱阴离子交换树脂及碱性洗脱剂的离子排阻/阴离子交换色谱法同时测定NH4+ ，NO2-和NO3-（英文）

Ion-exclusion/anion-exchange chromatography(IEC/AEC) on a combination of a strongly basic anion-exchange resin in the OH——form with basic eluent has been developed.The separation mechanism is based on the ion-exclusion/penetration effect for cations and the anion-exchange effect for anions to anion-exchange resin phase.This system is useful for simultaneous separation and determination of ammonium ion(NH+4),nitrite ion(NO-2),and nitrate ion(NO-3) in water samples.The resolution of analyte ions can be manipulated by changing the concentration of base in eluent on a polystyrene-divinylbenzene based strongly basic anion-exchange resin column.In this study,several separation columns,which consisted of different particle sizes,different functional groups and different anion-exchange capacities,were compared.As the results,the separation column with the smaller anion-exchange capacity(TSKgel Super IC-Anion) showed well-resolved separation of cations and anions.In the optimization of the basic eluent,lithium hydroxide(LiOH) was used as the eluent and the optimal concentration was concluded to be 2 mmol/L,considering the resolution of analyte ions and the whole retention times.In the optimal conditions,the relative standard deviations of the peak areas and the retention times of NH+4,NO-2,and NO-3 ranged 1.28%-3.57% and 0.54%-1.55%,respectively.The limits of detection at signal-to-noise of 3 were 4.10 μmol/L for NH+4,1.87 μmol/L for NO-2 and 2.83 μmol/L for NO-3.     

Multiferroics by rational design: implementing ferroelectricity in molecule-based magnets

Multiferroic materials: A novel class of multiferroics based on organic-inorganic hybrid materials is synthesized. The ferromagnetic properties originate from the coordination network, whereas the ferroelectricity results from the polar organic ions (see picture, M=magnetization and P=polarization).     

Structure–Activity Studies on the Fluorescent Indicator in a Displacement Assay for the Screening of Small Molecules Binding to RNA

A series of xanthone and thioxanthone derivatives with aminoalkoxy substituents were synthesized as fluorescent indicators for a displacement assay in the study of small‐molecule–RNA interactions. The RNA‐binding properties of these molecules were investigated in terms of the improved binding selectivity to the loop region in the RNA secondary structure relative to 2,7‐bis(2‐aminoethoxy)xanthone (X2S) by fluorimetric titration and displacement assay. An 11‐mer double‐stranded RNA and a hairpin RNA mimicking the stem loop IIB of Rev response element (RRE) RNA of HIV‐1 mRNA were used. The X2S derivatives with longer aminoalkyl substituents showed a higher affinity to the double‐stranded RNA than the parent molecule. Introduction of a methyl group on the aminoethoxy moiety of X2S effectively modulated the selectivity to the RNA secondary structure. Methyl group substitution at the C1′ position suppressed the binding to the loop regions. Substitution with two methyl groups on the amino nitrogen atom resulted in reducing the affinity to the double‐stranded region by a factor of 40 %. The effect of methyl substitution on the amino nitrogen atom was also observed for a thioxanthone derivative. Titration experiments, however, suggested that thioxanthone derivatives showed a more prominent tendency of multiple binding to RNA than xanthone derivatives. The selectivity index calculated from the affinity to the double‐stranded and loop regions suggested that the N,N‐dimethyl derivative of X2S would be suitable for the screening of small molecules binding to RRE.     

A novel quinoline alkaloid possessing a 7-benzyl group from the centipede, Scolopendra subspinipes.

The novel quinoline alkaloid scolopendrine was isolated from the centipede, Scolopendra subspinipes mutilans L. Koch. The structure was determined to be 2-hydroxy-7-[(4-hydroxy-3-methoxyphenyl)methyl]-3-methoxy-8-quinolyl sulfate on the basis of high-resolution electron-spray ionization mass spectroscopy and two-dimensional NMR spectral data. Unlike quinoline alkaloids so far reported, scolopendrine is unique in having a 7-benzyl moiety in the quinoline ring.     

Kinetic analysis of distribution of weak acid in an oil-gelatin microcapsule/water system studied by microcapillary injection and microabsorption methods.

The distribution of anthracene-9-carboxylic acid across dibutyl phthalate/gelatin-membrane/water interface of a single microcapsule was analyzed using microcapillary manipulation and microabsorption methods. The partitioning ratio and the distribution rate in the microcapsule/water system were measured for various pH values in the water phase. Results were compared with those in the dibutyl phthalate/water system in the absence of the gelatin membrane. The distribution rate could be analyzed on the basis of a first-order type reaction. The observed rate constant was linearly proportional to the inverse of the microcapsule radius, indicating that the distribution rate is limited by interfacial mass transfer. Analysis of the pH dependence of the interfacial mass transfer rate suggests that the mass transfer of the neutral species of anthracene-9-carboxylic acid (AnH) competes with the ion transfer of the dissociated species (An-) at the liquid/liquid interface in the gelatin membrane of the microcapsule.     

Iridium complex-catalyzed addition of water and alcohols to non-activated terminal alkynes

The addition of water and alcohols to non-activated terminal alkynes was found to be promoted by an iridium complex combined with Lewis acid and phosphite. Thus, terminal alkynes reacted with water or alcohols to give ketones or ketals, respectively, in good to excellent yields. α,ω-Diyne like 1,7-octadiyne was converted into 1-(2-methyl-cyclopent-1-enyl)ethanone through the intramoleculer aldol condensation of the resulting 2,7-octanedione induced by Lewis acid.