Hydroxyl Substitution Studies at the 5″‐Position in the Neomycin B Series: Introduction of a Phtalimide Group Under Mitsunobu Reaction Conditions

A phtalimido group can be readily introduced at the 5″‐position of N‐Boc ribostamycin 6 under Mitsunobu reaction conditions. However, in the case of N‐Boc neomycin B 4 a competitive bicyclization process occurred within the ring IV of the antibiotic, which led to compound 8, whose structure was fully elucidated by NMR spectroscopic methods. Accordingly, particular care must be exercised to achieve this chemical modification of the four‐ring antibiotic.     

Treatment and Determination of Organophosphorous Pesticides in Waste Water by Using Continuous Flow Methodologies Coupled On Line With High Performance Liquid Chromatography

Abstract

The treatment of waste water containing three organophosphorous pesticides: diazinon, azinphos-methyl and fenthion by using continuous flow methodologies coupled on line with HPLC-UV detection is presented.

Two continuous flow techniques: completely continuous flow and flow injection, both combined with two separation methods: liquid-liquid extraction and adsorption resins are discussed, as well as the influence of physical and chemical parameters on the analysis.

Adsorption resins seem to be more suitalbe for the treatment of waste water at low pesticide concentraions while liquid-liquid extraction is more selective.     

Nucleation and Growth of Chrysotile Nanotubes in H2SiO3/MgCl2/NaOH Medium at 90 to 300 °C

Herein, we report new insights into the nucleation and growth processes of chrysotile nanotubes by using batch and semi‐continuous experiments. For the synthesis of this highly carcinogenic material, the influences of temperature (90, 200, and 300 °C), Si/Mg molar ratio, and reaction time were investigated. From the semi‐continuous experiments (i.e., sampling of the reacting suspension over time) and solid‐state characterization of the collected samples by XRPD, TGA, FTIR spectroscopy, and FESEM, three main reaction steps were identified for chrysotile nucleation and growth at 300 °C: 1) formation of the proto‐serpentine precursor within the first 2 h of the reaction, accompanied by the formation of brucite and residual silica gel; 2) spontaneous nucleation and growth of chrysotile between about 3 and 8 h reaction time, through a progressive dissolution of the proto‐serpentine, brucite, and residual silica gel; and 3) Ostwald ripening growth of chrysotile from 8 to 30 h reaction time, as attested to by BET and FESEM measurements. Complementary results from batch experiments confirmed a significant influence of the reaction temperature on the kinetics of chrysotile formation. However, FESEM observations revealed some formation of chrysotile nanotubes at low temperatures (90 °C) after 14 days of reaction. Finally, doubling the Si/Mg molar ratio promoted the precipitation of pure smectite (stevensite‐type) under the same P (8.2 MPa)/T (300 °C)/pH (13.5) conditions.     

DFT study of antioxidant molecules from traditional Japanese and Chinese teas: comparing allylic and phenolic antiradical activity

Structural Chemistry - Quantum chemistry calculations were performed to compare the reactivity indexes obtained within the conceptual density functional theory of phenolic and allyl-phenolic...     

In‐Situ Growth and Immobilization of CdS Nanoparticles onto Functionalized MoS2: Preparation,Characterization and Fabrication of Photoelectrochemical Cells

A facile strategy for the controllable growth of CdS nanoparticles at the periphery of MoS₂ en route the preparation of electron donor‐acceptor nanoensembles is developed. Precisely, the carboxylic group of α‐lipoic acid, as addend of the modified MoS₂ obtained upon 1,2‐dithiolane functionalization, was employed as anchor site for the in situ preparation and immobilization of the CdS nanoparticles in an one‐pot two‐step process. The newly prepared MoS₂/CdS hybrid material was characterized by complementary spectroscopic, thermal and microscopy imaging means. Absorption spectroscopy was employed to register the formation of MoS₂/CdS, by observing a broad shoulder centered at 420 nm due to CdS nanoparticles, while the excitonic bands of MoS₂ were also evident. Moreover, based on the efficient quenching of the characteristic fluorescence emission of CdS at 725 nm by the presence of MoS₂, strong electronic interactions at the excited state between the two species within the ensemble were identified. Photoelectrochemical assays of MoS₂/CdS thin‐film electrodes revealed a prompt, steady and reproducible anodic photoresponse during repeated on‐off cycles of illumination. A significant zero‐current photopotential of ?540 mV and an anodic photocurrent of 1 μA were observed, underlining improved charge‐separation and electron transport from CdS to MoS₂. The superior performance of the charge‐transfer processes in MoS₂/CdS is of direct interest for the fabrication of photoelectrochemical and optoelectronic devices.     

Specific rearrangement reactions of acetylated lysine containing peptide bn (n = 4–7) ion series

Characterization of ε‐N‐acetylated lysine containing peptides, one of the most prominent post‐translational modifications of proteins, is an important goal for tandem mass spectrometry experiments. A systematic study for the fragmentation reactions of b ions derived from ε‐N‐acetyllysine containing model octapeptides (K_AcYAGFLVG and YAK_AcGFLVG) has been examined in detail. Collision‐induced dissociation (CID) mass spectra of b_n (n = 4–7) fragments of ε‐N‐acetylated lysine containing peptides are compared with those of N‐terminal acetylated and doubly acetylated (both ε‐N and N‐terminal) peptides, as well as acetyl‐free peptides. Both direct and nondirect fragments are observed for acetyl‐free and singly acetylated (ε‐N or N‐terminal) peptides. In the case of ε‐N‐acetylated lysine containing peptides, however, specific fragment ions (m/z 309, 456, 569 and 668) are observed in CID mass spectra of b_n (n = 4–7) ions. The CID mass spectra of these four ions are shown to be identical to those of selected protonated C‐terminal amidated peptides. On this basis, a new type of rearrangement chemistry is proposed to account for the formation of these fragment ions, which are specific for ε‐N‐acetylated lysine containing peptides. Consistent with the observation of nondirect fragments, it is proposed that the b ions undergo head‐to‐tail macrocyclization followed by ring opening. The proposed reaction pathway assumes that b_n (n = 4–7) of ε‐N‐acetylated lysine containing peptides has a tendency to place the K_Ac residue at the C‐terminal position after macrocyclization/reopening mechanism. Then, following the loss of CO, it is proposed that the marker ions are the result of the loss of an acetyllysine imine as a neutral fragment. Copyright © 2014 John Wiley & Sons, Ltd.     

Spectrofluorimetric determination of beryllium based on the inclusion complex of 1-amino-4-hydroxyanthraquinone with β-cyclodextrin as ligand

The use of the inclusion complex of 1-amino-4-hydroxyanthraquinone (AHA) in the internal cavity of β-cyclodextrin is compared with AHA alone as a ligand for the spectrofluorimetric determination of beryllium. The organizing ability of the cyclodextrin medium and the protection of the ligand from the micro-environment confers increased sensitivity, selectivity and detection limit, and allows the determination of 10–70 ng ml^?1 beryllium, compared to 60–500 ng ml^?1 in the absence of the cyclodextrin.     

Gold(I) complexes with thiolate and triphenylphosphine ligands

The reaction of [AuCl(PPh₃)] with Pb(SR)₂(R = C₂H₅, C₆H₅, CH₂C₆H₅, C₆F₅, C₆H₂Me₃-2,4,6, Prⁱ and Bu^t) provides a clean method to obtain complexes of the type [Au(SR)(PPh₃)] in good yields. The new compounds have been characterized by IR, ¹H, ³¹P, ¹⁹F and ³¹C NMR. A study by FAB mass spectrometry indicates that an ion-molecule aggregation process takes place.     

n-ary fragmentation model with nearest point flaw and maximal net force fracture

Through the distinction between “real” and “virtual” links between the nodes of a graph, we develop a set of simple rules leading to scale-free networks with a tunable degree distribution exponent. Albeit sharing some similarities with preferential attachment, our procedure is both faster than a naïve implementation of the Barabási and Albert model and exhibits different clustering properties. The model is thoroughly studied numerically and suggests that reducing the set of partners a node can connect to is important in seizing the diversity of scale-free structures.