Novel tocopheryl compounds. Part 16: Nitration of α-tocopheryl acetate—a mechanistic study

The reaction of α-tocopheryl acetate (vitamin E acetate, 3) with concentrated nitric acid proceeds according to a non-radical, two-step mechanism, producing 5-nitromethyl-γ-tocopheryl acetate (4) in good yields. In the first step, oxidation of 3 affords a benzylic cation intermediate (8), which in the second step adds nitrite to give 4. The acetyl group, which stabilizes intermediate 8 intramolecularly, remains bound to the tocopheryl moiety throughout the reaction.     

Degradation of cellulosic key chromophores by ozone: a mechanistic and kinetic study

Cellulose - Chromophores, colored substances of rather high stability that reduce brightness, are present in all kinds of cellulosic products, such as pulp, fibers, aged cellulosic material, and...     

The influence of alkaline reserve on the aging behavior of book papers

Degradation of cellulose under alkaline conditions is involved either involuntarily or deliberately in many different cellulose processing steps, such as pulping, bleaching, or aging within the viscose process, and the underlying chemistry has been the topic of numerous studies. When it comes to aging under alkaline conditions—either natural or accelerated (artificial)—the degradation processes are by far less investigated and understood. A prominent example of moderately alkaline cellulosic material is deacidified book paper from libraries which had undergone a mass-deacidification treatment. We studied their aging behavior under accelerated conditions in comparison to non-deacidified duplicates in order to better understand how the alkaline reserve, which was introduced by the deacidification treatment, affects the stability of the books on the long run. GPC analysis of cellulose and determination of carbonyl functionalities were performed, which were critical parameters to achieve a deeper insight into hydrolytic and oxidative changes of cellulose structure upon deacidification treatment and subsequent aging. Also, model book papers impregnated with different amounts of alkaline reserve were used to support the findings from the original book samples. Hydrolytic degradation rates of the original book papers were significantly reduced after mass deacidification compared to the non-deacidified duplicates. The beneficial effect of mass deacidification on cellulose stability was found to be strongly related to the amount of alkaline reserve deposited, independent of varying parameters of book papers. Although some indication of alkali-induced β-elimination was found (a minor decrease of the along-chain carbonyl content in the original deacidified book papers during aging), it did not occur to an extent that significantly influenced the molar mass of cellulose. The beneficial effect of retarded hydrolytic degradation by mass deacidification thus clearly outweighed possible negative alkalinity effects of the deposited alkaline reserve.     

Compactification of patterns by a singular convection or stress

A wide variety of propagating disturbances in physical systems are described by equations whose solutions lack a sharp propagating front. We demonstrate that presence of particular nonlinearities may induce such fronts. To exemplify this idea, we study both dissipative u_{t}+ partial differential_{x}f(u)=u_{xx} and dispersive u_{t}+ partial differential_{x}f(u)+u_{xxx}=0 patterns, and show that a weakly singular convection f(u)=-u;{alpha}+u;{m}, 0相似文献   

The Diversity of a Polyclonal FluCell-SELEX Library Outperforms Individual Aptamers as Emerging Diagnostic Tools for the Identification of Carbapenem Resistant Pseudomonas aeruginosa

Textbook procedures require the use of individual aptamers enriched in SELEX libraries which are subsequently chemically synthesized after their biochemical characterization. Here we show that this reduction of the available sequence space of large libraries and thus the diversity of binding molecules reduces the labelling efficiency and fidelity of selected single aptamers towards different strains of the human pathogen Pseudomonas aeruginosa compared to a polyclonal aptamer library enriched by a whole-cell-SELEX involving fluorescent aptamers. The library outperformed single aptamers in reliable and specific targeting of different clinically relevant strains, allowed to inhibit virulence associated cellular functions and identification of bound cell surface targets by aptamer based affinity purification and mass spectrometry. The stunning ease of this FluCell-SELEX and the convincing performance of the P. aeruginosa specific library may pave the way towards generally new and efficient diagnostic techniques based on polyclonal aptamer libraries not only in clinical microbiology.     

Synthesis of Polyanionic Cellulose Carbamates by Homogeneous Aminolysis in an Ionic Liquid/DMF Medium

Polyanionic cellulose carbamates were synthesized by rapid and efficient homogeneous aminolysis of cellulose carbonate half-esters in an ionic liquid/DMF medium. Cellulose bis-2,3-O-(3,5-dimethylphenyl carbamate), as a model compound, reacted with different chloroformates to cellulose carbonates. These intermediates were subjected to aminolysis, for which both the reactivity of different chloroformates towards C6-OH and the reactivity/suitability of the respective carbonate half-ester in the aminolysis were comprehensively studied. Phenyl chloroformate and 4-chlorophenyl chloroformate readily reacted with C6-OH of the model cellulose derivative, while 4-nitrophenyl chloroformate did not. The intermediate 4-chlorophenyl carbonate derivative with the highest DS (1.05) was then used to evaluate different aminolysis pathways, applying three different amines (propargyl amine, β-alanine, and taurine) as reactants. The latter two zwitterionic compounds are only sparingly soluble in pure DMF as the typical reaction medium for aminolysis; therefore, several alternative procedures were suggested, carefully evaluated, and critically compared. Solubility problems with β-alanine and taurine were overcome by the binary solvent system DMF/[EMIM]OAc (1:1, v/v), which was shown to be a promising medium for rapid and efficient homogeneous aminolysis and for the preparation of the corresponding cellulose carbamate derivatives or other compounds that are not accessible by conventional isocyanate chemistry. The zwitterionic cellulose carbamate derivatives presented in this work could be promising chiral cation exchangers for HPLC enantiomer separations.     

MR imaging of liver abscesses; application of Gd-DTPA

The potential utility of Gd-DTPA contrast enhancement of MR images in the evaluation of liver abscesses was assessed in rodents. Twelve rats with surgically implanted sterile liver abscesses were imaged at various stages of focal hepatic inflammation, 48 hours, 4 days, 7 days, 14 days and 21 days after lesion induction. Spin echo images, acquired before and repeatedly after intravenous injection of 0.2 mmol/kg Gd-DTPA, demonstrated improvement of the lesion-to-background contrast ranging from 2% to 40% depending on the stage of the disease. The enhancement pattern also varied with abscess evolution. Two, four and seven-day-old abscesses typically showed a ring enhancement, whereas two- and three-week-old abscesses presented largely homogeneously enhancing lesions. In the earlier lesions, contrast enhanced rim surrounding the low intensity center corresponded histologically to the formation of a capsule consisting of fibrous tissue and inflammatory cells. The center was necrotic. Data show that abscesses can be detected on images acquired with long repetition and echo times without injection of Gd-DTPA. The administration of Gd-DTPA, however, improved the lesion-to-background contrast and helped to define the abscess capsule evolution.     

Stabilization and first direct spectroscopic evidence of the o-quinone methide derived from vitamin E

[reaction: see text] The o-quinone methide (2) derived from vitamin E (1) can be stabilized at low temperatures in a complex with the highly polar N-methylmorpholine-N-oxide (5). The lifetime of 2 can thus be prolonged from less than 10 s to several minutes. In the complex formed, 2 adopts a zwitterionic, aromatic structure with the exocyclic methylene group in perpendicular arrangement to the ring plane, stabilized by the negatively charged oxygen in 5.     

Compact and almost compact breathers: a bridge between an anharmonic lattice and its continuum limit

We demonstrate that certain strictly anharmonic one-dimensional FPU lattices with a suitable quartic site potential appended support almost-compact discrete breathers over a macroscopic localized domain that is essentially fixed independently of the sparseness of the lattice. Beyond that domain the discrete breather tails decay at a double-exponential rate in the lattice-cell index, becoming truly compact in the continuum limit. Furthermore, the discrete breather is stable for amplitudes below a sharp threshold that depends on the sparseness of the lattice. For the two-dimensional version of the problem, the continuum limit of a planar hexagonal lattice with a purely quartic interaction potential begets an isotropic multidimensional nonlinear wave equation. When a quartic site potential of the appropriate sign is appended, the continuum equation has a compactly supported radial breather solution.