Poly‐ε‐Lysine Modified Nanocarbon Film Electrodes for LPS Detection

We developed an electrochemical system for detecting lipopolysaccharide (LPS) that uses an ultraflat nanocarbon film electrode modified with poly‐ε‐lysine with a high affinity to LPS. LPS was captured on the modified electrode, and then ferrocene labeled polymyxin B (FcPMB) was captured on the LPS adsorbed electrode via the LPS‐PMB affinity interaction. The adsorbed FcPMB provided an amplified response with Fe²⁺ ions, and the current response was dependent on the amount of captured LPS (LOD=2.0 ng/mL). This was due to the efficient accumulation of the obtained current for LPS and the very low noise made possible by the ultraflat surface.     

Improved Photobleaching for (1,10-phenanthroline)tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) Particle Embedded in Sol-Gel Derived Glass Film

In this research, we investigated improved photobleaching characteristics of (1,10-phenanthroline)tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]europium(III) by forming nano-particles embedded into a sol-gel derived silica glass film by a conventional sol-gel process. The relative photoluminescence intensities after the UV irradiation for 90 min were 88, 76, and 67% for nano-particles in the sol-gel derived glass film, powders in the sol-gel derived glass film, and raw powders, respectively. This result indicates that the phtobleaching of this Eu-complex can improved by forming nano-partcile structures by a reprecipitation method and embedding in the sol-gel derived silica glass.     

Improved Crystallinity of Poly(3-hexylthiophene-2,5-diyl):[6,6]-Phenyl-C61 Butyric Acid Methyl Ester Film by Pulsed Electrospray Deposition

We investigated crystallinity parameters and ordering domains of poly(3-hexylthiophene-2,5-diyl) blended in [6,6]-phenyl-C₆₁-butyric acid methyl ester films, which were fabricated by pulsed electrospray deposition methods. The crystallinity parameter and the ordering domain were estimated from Raman and optical absorption spectra, respectively. As a result, they were improved with decreasing the off time of pulse voltage, corresponding to the slow evaporation speed of solvent. In addition, both the space-charge limited current mobility and the photoconversion efficiency showed same trend. A highest photoconversion efficiency of 1.11 % was achieved without the thermal annealing process after depositing the active layer.     

Synthesis of α‐Dawson‐Type Silicotungstate [α‐Si2W18O62]8− and Protonation and Deprotonation Inside the Aperture through Intramolecular Hydrogen Bonds

The design of structurally well‐defined anionic molecular metal–oxygen clusters, polyoxometalates (POMs), leads to inorganic receptors with unique and tunable properties. Herein, an α‐Dawson‐type silicotungstate, TBA₈[α‐Si₂W₁₈O₆₂] ? 3 H₂O ( II ) that possesses a ?8 charge was successfully synthesized by dimerization of a trivacant lacunary α‐Keggin‐type silicotungstate TBA₄H₆[α‐SiW₉O₃₄] ? 2 H₂O ( I ) in an organic solvent. POM II could be reversibly protonated (in the presence of acid) and deprotonated (in the presence of base) inside the aperture by means of intramolecular hydrogen bonds with retention of the POM structure. In contrast, the aperture of phosphorus‐centered POM TBA₆[α‐P₂W₁₈O₆₂]?H₂O ( III ) was not protonated inside the aperture. The density functional theory (DFT) calculations revealed that the basicities and charges of internal μ₃‐oxygen atoms were increased by changing the central heteroatoms from P⁵⁺ to Si⁴⁺, thereby supporting the protonation of II . Additionally, II showed much higher catalytic performance for the Knoevenagel condensation of ethyl cyanoacetate with benzaldehyde than I and III .     

Dehydration‐fragmentation mechanism of cathinones and their metabolites in ESI‐CID

Various cathinone‐derived designer drugs (CATs) have recently appeared on the drug market. This study examined the mechanism for the generation of dehydrated ions for CATs during electrospray ionization collision‐induced dissociation (ESI‐CID). The generation mechanism of dehydrated ions is dependent on the amine classification in the cathinone skeleton, which is used in the identification of CATs. The two hydrogen atoms eliminated during the dehydration of cathinone (primary amine) and methcathinone (secondary amine) were determined, and the reaction mechanism was elucidated through the deuterium labeling experiments. The hydrogen atom bonded to the amine nitrogen was eliminated with the proton added during ESI, in both of the tested compounds. This provided evidence that CATs with tertiary amine structures (such as dimethylcathinone and α‐pyrrolidinophenones [α‐PPs]) do not undergo dehydration. However, it was shown that the two major tertiary amine metabolites (1‐OH and 2″‐oxo) of CATs generate dehydrated ions in ESI‐CID. The dehydration mechanisms of the metabolites of α‐pyrrolidinobutiophenone (α‐PBP) belongs to α‐PPs were also investigated. Stable‐isotope labeling showed the dehydration of the 1‐OH metabolite following a simple mechanism where the hydroxy group was eliminated together with the proton added during ESI. In contrast, the dehydration mechanism of the 2″‐oxo metabolite involved hydrogen atoms in three or more locations along with the carbonyl group oxygen, indicating that dehydration occurred via multiple mechanisms likely including the rearrangement reaction of hydrogen atoms. These findings presented herein indicate that the dehydrated ions in ESI‐CID can be used for the structural identification of CATs.     

From

Let be a space of finite type. Set as usual, and define the mod support of by for 0.$"> Call sparse if there is no with

Then we show the relation for any finite type space with being sparse.

As a special case, we have and the main theorem of Ravenel, Wilson and Yagita is also generalized in terms of the mod support.

     

Identification of a Single Phosphorylation Site Within Octopus Rhodopsin

Abstract— Light-dependent phosphorylation of rhodopsin (Rho) is a first step in the desensitization of the signaling state of the receptor during vertebrate and invertebrate visual transduction. We found that only ³⁵⁸Ser of the photoac-tivated octopus Rho (oRho*) was phosphorylated by octopus rhodopsin kinase (oRK). Tryptic truncation of the C-terminal PPQGY repeats of oRho that follow the phosphorylation region did not influence spectral or G-protein activation properties of oRho but abolished phos phorylation. Despite significant structural differences between oRK and mammalian RK, these results provide i further evidence of the importance of singly phosphorylated species of Rho* in the generation of arrestin binding sites.     

Synthetic studies leading to DE-ring analogs of camptothecin

A synthetic scheme leading to an isomeric DE ring ( 14 ) of the anti-tumor alkaloid, camptothecin, has been achieved. However, the method failed to give the correct pyridone lactone ( 2 ) found in this alkaloid.     

Highly effective synthetic methods for substituted 2-arylbenzofurans using [3,3]-sigmatropic rearrangement: short syntheses of stemofuran a and eupomatenoid 6

A new and efficient synthesis of 2-arylbenzofurans has been achieved via a route involving acylation and subsequent [3,3]-sigmatropic rearrangement of oxime ethers. Its synthetic utility is demonstrated by a short synthesis of stemofuran A and eupomatenoid 6 in which no procedure for protection of the phenolic hydroxyl groups is needed. [reaction--see text]