Ambient pressure chemical hydrogenation using p-toluene sulfonyl hydrazide (TSH) via thermal diimide formation (N2H2) permitted reduction of double bonds of poly(myrcene) (poly[Myr]) and poly(farnesene) (poly[Far]). Both pendent and backbone double bonds in poly(Myr) (Mn = 56 kg/mol) and poly(Far) (Mn = 62 kg/mol) synthesized by conventional free radical polymerization were hydrogenated to almost completion. Furthermore, TSH semi-batch addition efficiently hydrogenated double bonds, while avoiding undesired autohydrogenation of diimides that occurred in batch mode. Thermal stability improved for hydrogenated poly(Myr) and poly(Far), where temperature at 10% weight loss (T10%) increased from 188 to 404°C for poly(Myr) and from 310 to 379°C for poly(Far). Tgs of poly(Myr) and poly(Far) also increased by about 10–25°C, indicating increased stiffness after hydrogenation. Finally, viscosities of poly(Myr) and poly(Far) were also increased after hydrogenation, and a greater increase was observed for poly(Myr) (by two orders of magnitude from 102 to 104 Pa s) due to its Mn being much higher than its entanglement molecular weight. Poly(Far) viscosity only increased by 1.5 times after hydrogenation (~104 Pa s), comparable to the poly(Myr) after hydrogenation, suggesting unsaturated poly(Far) was more entangled than unsaturated poly(Myr) because of its longer side chains. 相似文献
Sole lineshape estimation of non-parametrically computed higher-order derivatives of spectral envelopes in different modes (complex, real, imaginary, magnitude) is investigated. The processed time signals are sums of complex attenuated exponentials (harmonics). The peak parameters of the derivative spectra are directly connected to those of the customary (non-derivative) absorption lineshapes. Crucially, this permits the reconstruction of the latter from the former parameters (the latter are sought since they are unknown, whereas the former are extractable from the derivative envelopes). The cross-checking relationships of the lineshapes for the magnitude modes with the real and imaginary parts of the complex-valued envelopes (total shape spectra) are established. The explicit procedure and the necessary analytical expressions are presented for reconstruction of the exact locations, widths and heights of all the retrieved physical resonances (spectral peaks). These facets are illuminated in the derivative fast Padé transform (dFPT) using its non-parametric version, i.e. without solving the quantification problem (no polynomial rooting, no tackling of eigen-value problems, etc.). Two kinds of illustrations for derivative spectra are reported. One deals with the general Breit-Wigner resonance formula and its first three derivatives. The other is concerned with the dFPT in clinical diagnostics of relevance to breast cancer detection by magnetic resonance spectroscopy. A systematic parallel between these two examples is drawn to highlight, in a stepwise manner, the role of paramount importance played by derivative lineshapes, especially for disentangling overlapping resonances that invariably plague all quantitative analyses of spectra. 相似文献
Electron impact excitation rate coefficients for singlet and triplet electronic states of the carbon monoxide molecule have been calculated under non-equilibrium conditions in the presence of radio-frequency electric field. A Monte Carlo simulation of electron transport has been performed in order to determine non-equilibrium electron energy distribution functions within one period of applied electric field. By using these distribution functions and corresponding cross sections, the excitation rate coefficients have been calculated for all electronic states of CO in the frequency range from 13.56 up to 500 MHz, at reduced root mean square electric field values ranging from 200 to 700 Td. We expect these rates to be valuable for modeling radio-frequency CO plasmas since excited neutrals exhibit greater chemical reactivity than neutrals in ground electronic state, hence altering many properties of plasma. 相似文献
A novel sustainable and eco-friendly procedure simultaneously combining the use of ultrasound irradiation and hydroxypropyl-β-cyclodextrin (HPβCD) complexation was used to extract phytochemicals from Lotus corniculatus and to prepare flavonoid rich extract having potential as substrate reduction therapy of mucopolysaccharidosis type III (MPS III), a rare autosomal recessive lysosomal storage disorder. For that instance, Box-Behnken design and response surface methodology was employed to statistically assess the influence of HPβCD concentration, ultrasonic power, and extraction time on the total phenolic compounds, total flavonoids, total phenolic acids and radical scavenging activity (RSA) of the extracts prepared, chosen as the responses indicative of the product quality and performance. The potential of such optimised extract to modulate accumulation of gylcosoaminoglycans (GAGs) was evaluated on the fibroblast obtained from patients suffering from MPS type III. Optimized extract prepared by 45 min extraction using HPβCD at concentration of 20 mM and ultrasonic irradiation of 648 W was rich in flavonoids (1.36 mg/mL) and showed notable RSA of 1.04 mg/mL. Freeze-dried extract, at concentration of 3 and 6 µg/mL, reduced GAG levels in skin fibroblasts by 33.97 and 50.08%, respectively, without any toxic effects at given doses, showing a potential to be considered as a part of the substrate reduction therapy of MPS III. 相似文献
A simple one-pot synthesis of new ferrocene-containing 1,3-thiazinan-2-imines from 3-arylamino-1-ferrocenylpropan-1-ols and phenyl isothiocyanate has been developed. The key intermediate β-hydroxy thioureas were generated in situ using ultrasound irradiation and subsequent cyclization was achieved by the addition of acetic acid. The scope of the reaction towards various 3-arylamino-1-ferrocenylpropan-1-ols has been explored and the corresponding 3-aryl-6-ferrocenyl-N-phenyl-1,3-thiazinan-2-imines were obtained in moderate to high yields (52–90%). 相似文献
The authors report on a novel sorbent (thermally treated natural zeolite; clinoptilolite) for use in dispersive micro-solid phase extraction (D-μ-SPE) of polycyclic aromatic hydrocarbons (PAHs) from water samples. The method was applied to the D-μ-SPE of 16 priority PAHs which then were quantified by gas chromatography with mass spectrometric detection (GC-MS). The method was validated in terms of specificity and selectivity, linearity and linear range, accuracy, precision, uncertainty, limits of detection and quantification. Figures of merit include (a) linear analytical ranges between 2.08 and 208 ppb, and (b) detection limits in the range from 0.01 to 0.92 ppb. The method was successfully applied to the determination of PAHs in river waters.
Graphical abstract Schematic representation of dispersive micro-solid phase extraction (D-μ-SPE) of trace levels of PAHs in water samples by using thermally treated clinoptilolite as sorbent prior to gas chromatography-mass spectrometry analysis (GC-MS).
Phytochemical analysis by GC and GC/MS of the essential oil samples obtained from fresh shoots and flowers of Saponaria officinalis L. allowed the identification of 96 components in total, comprising 94.7% and 86.0% of the total oils compositions, respectively. Regarding the shoots essential oil, the major of 87 identified volatile compounds were phytol (14.1%), tricosane-6,8-dione (13.4%), patchouli alcohol (7.9%) and tricosane (7.2%), whereas patchouli alcohol (20.0%), heneicosane (11.5%) and tricosane (8.4%) were dominant among the 66 volatiles in the flower oil. Nonterpenoid compounds had the highest contribution in S. officinalis shoots essential oil (53.7%), while in the flower oil, constituents were almost evenly distributed between the oxygenated sesquiterpenoid (41.2%) and nonterpenoid compounds (39.5%). 相似文献
A novolac phenol-formaldehyde resin was investigated via the thermally stimulated depolarization current, using integral and partial measurements in the temperature range from 137 to 270 K. Tow broadened peaks, assigned as Β1, and Β2, appeared at about 160 and 190 K. The influence of water and ¯Mn was investigated. The activation energy Eavs. T relationship was analysed, and a search was made for compensation phenomena. The distribution of the relaxing dipolesN vs. Ea was approximated. Three different relaxation ranges were distinguished. All the motions were attributed to the rotation of the phenyl rings. The differences found are due to the heterogeneity in the resin. Contamination with water increases the polarizability, decreases the structure differences and relieves the motions in the resin. A resin with a smaller ¯Mn exhibits a higher polarizability and a decreases in structure variety. 相似文献