Synthesis,tautomerism and diels-alder reactions of 1, 4-dihydroxy-9, 10-anthraquinon-9-imines

The ammonolysis of quinizarin and simple derivatives thereof affords 9-imino-derivatives, the tautomeric forms of which act as dienophiles in Diels-Alder reactions to yield tetracyclic compounds of potential value as anthracyclinone precursors.     

Nonmonotone inexact restoration approach for minimization with orthogonality constraints

Numerical Algorithms - Minimizing a differentiable function restricted to the set of matrices with orthonormal columns finds applications in several fields of science and engineering. In this...     

Fluorescent boron Schiff bases dyes for staining silk fibroin: Green synthesis,structural characterization,DFT, and photophysical properties

Five novel organoboron complexes were synthesized in just 15 min via microware irradiation, by one pot multicomponent reactions between diverse aryl aldehydes with benzoylhydrazide, or 4‐nitrobenzoylhidrazine and diphenyl boronic acid, in a 1:1:1 ratio in benzene. The products were characterized by ¹H, ¹³C, ¹¹B NMR, UV, IR, spectroscopy and high‐resolution mass spectrometry (HRMS). The molecular structure was also determined by single‐crystal X‐ray diffraction for two complexes, which showed the tetra‐coordination of the boron atoms giving rise to distorted tetrahedral molecular geometry with a strong intermolecular C‐H···π interactions. In spite of the low quantum yields exhibited by the series in solution, some complexes stained uniformly the silk fibroins emitting enough fluorescence to allow its characterization by confocal microscopy. Boron as chelate center of the five complexes resulted not to be toxic for B16F10 cells, these compounds are appropriate for their used in medical applications.     

Thermal properties,nanoscopic structure and swelling behavior of chitosan/(ureasil–polyethylene oxide hybrid) blends

In this work, the effect of chitosan blending on the thermal properties, nanoscopic structure and swelling behavior of ureasil–polyethylene oxide (U-PEO) hybrid materials was examined. Materials were prepared by the sol–gel route using acid catalysts, and the effect of acid (hydrochloric or acetic acid) was also examined. Differential scanning calorimetry results showed that chitosan addition did not provoke appreciable changes in the thermal behavior of the U-PEO. Thermogravimetric curves did not show changes in thermal stability resulting from chitosan blending but were depended on the type of acid catalyst. Small-angle X-ray scattering and nuclear magnetic resonance spectroscopy techniques were used for studying nanoscopic and inner structures, showing the existence of two structural levels and differences in polycondensation degrees. All samples presented fast water uptake with the same initial swelling rate and with a non-Fickian or anomalous transport mechanism. Swelling degree was higher in hybrids prepared with HCl, which possessed less branched siloxane cross-link nodes species, therefore lower polycondensation degree. Also, the magnitude of swelling decreased for hybrids blended with chitosan, which provides a means of tailoring the water uptake by the ureasil–PEO hybrid and to potentiate the control of the release profile of drugs incorporated in these materials.     

Surface characterisation of plasma-modified poly(ethylene terephthalate)

This paper reports the modifications produced by nitrogen and helium cold plasmas on the surface of PET. The changes have been studied by diffuse reflectance Fourier transform spectroscopy (DRIFTS), atomic force microscopy (AFM) and inverse gas-solid chromatography (IGSC). Nitrogen and oxygen atoms seem to appear on the surface of PET as a consequence of the exposure to the atmosphere after the treatments with plasmas. AFM shows that both plasmas altered in different extent the surface of PET as they break the polymer chains producing low molecular products which appear as bumps on the surface. The surface area and the porosity of PET does not change by plasma treatments even after 15 min. The dispersive component of the surface free energy, gamma(s)(d), decreases after long treatments with nitrogen plasma whereas it remains almost unchanged after long treatment with helium plasma.     

Atomic-scale scanning tunneling microscopy study of plasma-oxidized ultrahigh-modulus carbon fiber surfaces

In the present work, scanning tunneling microscopy (STM) was employed to study the surface modification of ultrahigh modulus carbon fibers at the atomic level by oxygen plasma. As detected by STM, the distinctive feature of the fresh, untreated surface was the general presence of atomic-scale arrangements in different degrees of order (from atomic-sized spots without a clearly ordered disposition to triangular patterns identical to those typical of perfect graphite). Following fiber exposure to the plasma, the STM images showed evidence of the abstraction of carbon atoms from random locations on the fiber surface, giving rise to the development of defects (i.e., structural disorder), which in turn were the places where oxygen could be introduced during and after the plasma etching. It was observed that the most effective treatments in terms of extent of surface structural modification (disordering) and uniform introduction of oxygen were those carried out for just a few ( approximately 3) minutes. Considerably shorter exposures failed to provide a homogeneous modification and many locations on the fiber surface remained unaltered, retaining their original atomic-scale order, whereas longer treatments did not bring about further structural changes to the surface and only led to fiber consumption. These results are consistent with previous X-ray photoelectron spectroscopy measurements on these fibers and provide an atomic-level understanding of the saturation effect observed in the surface oxygen concentration of this and other types of carbon fibers with plasma oxidation. Such understanding may also prove helpful for the accurate control and optimization of fiber-matrix interaction in composite materials.     

Continuous flow system for lead determination by faas in spirituous beverages with solid phase extraction and on-line copper removal

A continuous flow system for the determination of lead in home made spirituous beverages was developed. The determination was based on the formation of a neutral chelate of the element with ammonium pyrrolidine dithiocarbamate, its adsorption onto a minicolumn packed with sodium faujasite type Y synthetic zeolite, followed by elution with methyl isobutyl ketone and determination by flame atomic absorption spectrometry. Ethanol and copper interfere strongly in the determination and therefore, must be separated prior to the analysis. Copper is removed by precipitation with rubeanic acid, while ethanol is eliminated by rotaevaporation. Sample solutions containing Pb²⁺ in the concentration range from 5 to 120 μg l⁻¹ at pH 2.5 could be analyzed, by using a preconcentration time of 3 min. Preconcentration factors from 80 to 140 were achieved for a sample volume of 6 ml and the detection limit varied from 1.4 to 3.5 μg l⁻¹, depending on the matrix composition. The relative standard deviations for 60 μg l⁻¹ Pb was 3.2% (n = 10) and the recovery of spikes (20, 40, 60 and 80 μg l⁻¹) added to the samples was estimated within 92–105% range, suggesting that lead can be quantitatively determined in such samples. Determining lead in several samples by an alternative technique further checked the accuracy. Finally, the concentrations of Pb²⁺ determined in 28 samples of Venezuelan spirituous beverages were in 12.6–370.0 μg l⁻¹ range, depending on the fermenting material based on different mixtures of agave, raw sugar cane and white sugar.     

Effects of oxygen and carbon dioxide plasmas on the surface of poly(ethylene terephthalate)

Poly(ethylene terephthalate) was exposed to oxygen and carbon dioxide plasmas for different periods of time. The surface-modified samples were characterized by infrared spectroscopy, atomic force microscopy, and inverse gas-solid chromatography. The main difference between both types of plasma was connected to the time scale of degradation, which was much faster when using oxygen plasma. Aggregate globular features were produced by different treatments due to chain scission and further recombination of evolved products. Oxygenated functionalities were introduced in significant amounts after long exposure times to the oxygen plasma. As a consequence, the specific component of the surface free energy was clearly observed to increase after these long treatments.