Thermal degradation kinetics and heat properties of cellulosic cigarette paper: influence of potassium carboxylate as combustion improver

Accurate determination of the thermal properties of cellulose is of particular significance in studying the mechanism of cellulosic cigarette paper combustion. This paper probes into the influence of four kinds of potassium carboxylates on the thermal degradation kinetics and the heat properties of cigarette paper through simultaneous thermogravimetric analysis (TGA) coupled with differential scanning calorimetry (DSC) measurement under air atmosphere. Reduced mass loss and mass loss rate, and increased solid residue for samples containing four potassium salts implied that potassium carboxylates may retard the formation of levoglucosan and volatiles by inhibiting the depolymerization reaction and simultaneously accelerate char formation by catalyzing the dehydration reaction. Kinetic parameters were analyzed based on three non-isothermal models available in literature. The results indicated that three modeling methods exhibit good consistency. A global activation energy range of 106–155 kJ mol^?1 was proposed for cigarette paper with potassium carboxylates. The four potassium salts studied considerably reduced the activation energy in the following descending order: potassium 1,2,3,4-butane tetracarboxylate (PBTCA) > citrate > gluconate > ascorbate. The heat properties of cigarette paper were also determined by integrating the DSC curves. The results demonstrated that both cellulose degradation and char oxidation have strong exothermic peaks. Cigarette paper samples with potassium salts have lower exothermic cellulose degradation process and higher exothermic char oxidation process, which were further confirmed by greater differences as the amounts of salt citrate or PBTCA increased.     

Spatiotemporal dynamics of lump solution to the (1 + 1)-dimensional Benjamin–Ono equation

Nonlinear Dynamics - This paper focuses on the finite-time synchronization problem for a kind of general complex networks with intrinsic time-varying delays and hybrid couplings (i.e., containing...     

Validated UPLC‐MS/MS method for determination of moclobemide in human brain cell supernatant and its application to bidirectional transport study

A simple and sensitive analytical method based on ultraperformance liquid chromatography–tandem mass spectrometry (UPLC‐MS/MS) has been developed for determination of moclobemide in human brain cell monolayer as an in vitro model of blood–brain barrier. Brucine was employed as the internal standard. Moclobemide and internal standard were extracted from cell supernatant by ethyl acetate after alkalinizing with sodium hydroxide. The UPLC separation was performed on an Acquity UPLC^TM BEH C₁₈ column (50 × 2.1 mm, 1.7 µm, Waters, USA) with a mobile phase consisting of methanol–water (29.5:70.5, v/v); the water in the mobile phase contained 0.05% ammonium acetate and 0.1% formic acid. Detection of the analytes was achieved using positive ion electrospray via multiple reaction monitoring mode. The mass transitions were m/z 269.16 → 182.01 for moclobemide and m/z 395.24 → 324.15 for brucine. The extraction recovery was 83.0–83.4% and the lower limit of quantitation (LLOQ) was 1.0 ng/mL for moclobemide. The method was validated from LLOQ to 1980 ng/mL with a coefficient of determination greater than 0.999. Intra‐ and inter‐day accuracies of the method at three concentrations ranged from 89.1 to 100.9% for moclobemide with precision of 1.1–9.6%. This validated method was successfully applied to bidirectional transport study of moclobemide blood–brain barrier permeability. Copyright © 2013 John Wiley & Sons, Ltd.     

Convergence in law to operator fractional Brownian motion of Riemann-Liouville type

In this paper, we extend the well-studied fractional Brownian motion of Riemann-Liouville type to the multivariate case, and the corresponding processes are called operator fractional Brownian motions of Riemann-Liouville type. We also provide two results on approximation to operator fractional Brownian motions of Riemann-Liouville type. The first approximation is based on a Poisson process, and the second one is based on a sequence of I.I.D. random variables.     

Synthesis and characterization of novel elastomeric poly(D,L-lactide urethane) maleate composites for bone tissue engineering

Here, we report the synthesis and characterization of a novel 4-arm poly(lactic acid urethane)-maleate (4PLAUMA) elastomer and its composites with nano-hydroxyapatite (nHA) as potential weight-bearing composite. The 4PLAUMA/nHA ratios of the composites were 1:3, 2:5, 1:2 and 1:1. FTIR and NMR characterization showed urethane and maleate units integrated into the PLA matrix. Energy dispersion and Auger electron spectroscopy confirmed homogeneous distribution of nHA in the polymer matrix. Maximum moduli and strength of the composites of 4PLAUMA/nHA, respectively, are 1973.31 ± 298.53 MPa and 78.10 ± 3.82 MPa for compression, 3630.46 ± 528.32 MPa and 6.23 ± 1.44 MPa for tension, 1810.42 ± 86.10 MPa and 13.00 ± 0.72 for bending, and 282.46 ± 24.91 MPa and 5.20 ± 0.85 MPa for torsion. The maximum tensile strains of the polymer and composites are in the range of 5–93%, and their maximum torsional strains vary from 0.26 to 0.90. The composites exhibited very slow degradation rates in aqueous solution, from approximately 50% mass remaining for the pure polymer to 75% mass remaining for composites with high nHA contents, after a period of 8 weeks. Increase in ceramic content increased mechanical properties, but decreased maximum strain, degradation rate, and swelling of the composites. Human bone marrow stem cells and human endothelial cells adhered and proliferated on 4PLAUMA films and degradation products of the composites showed little-to-no toxicity. These results demonstrate that novel 4-arm poly(lactic acid urethane)-maleate (4PLAUMA) elastomer and its nHA composites may have potential applications in regenerative medicine.     

Reduced matrix effects for anionic compounds with paired ion electrospray ionization mass spectrometry

It is well-known that matrix effects in high performance liquid chromatography coupled to electrospray ionization mass spectrometry (HPLC-ESI-MS) can seriously compromise quantitative analysis and affect method reproducibility. Paired ion electrospray ionization (PIESI) mass spectrometry is an approach for analyzing ultra-low levels of anions in the positive ion mode. This approach uses a structurally optimized ion pairing reagent to post-column associate with the anionic analyte, subsequently forming positively charged complexes. These newly formed complex ions are often more surface-active as compared to either the native anion or the ion pairing reagent. No studies have examined whether or not the PIESI approach mitigates matrix effects. Consequently, a controlled study was done using five analytes in highly controlled and reproducible synthetic groundwater and urine matrices. In addition, two different mass spectrometers (linear ion trap and triple quadrupole) were used. Compared to the negative ion mode, the PIESI-MS approach was less susceptible to matrix effects when performed on two different MS platforms. Using PIESI-MS, less dilution of the sample is needed to eliminate ionization suppression which, in turn, permits lower limits of detection and quantitation.     

Tailorable PC71BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High‐Performance Polymer Solar Cells

Despite being widely used as electron acceptor in polymer solar cells, commercially available PC₇₁BM (phenyl‐C₇₁‐butyric acid methyl ester) usually has a “random” composition of mixed regioisomers or stereoisomers. Here PC₇₁BM has been isolated into three typical isomers, α‐, β₁‐ and β₂‐PC₇₁BM, to establish the isomer‐dependent photovoltaic performance on changing the ternary composition of α‐, β₁‐ and β₂‐PC₇₁BM. Mixing the isomers in a ratio of α/β₁/β₂=8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC₇₁BM as photoactive layer (PTB7=poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]]). The three typical PC₇₁BM isomers, even though sharing similar LUMO energy levels and light absorption, render starkly different photovoltaic performances with average‐performing PCE of 1.28–7.44 % due to diverse self‐aggregation of individual or mixed PC₇₁BM isomers in the otherwise same polymer solar cells.     

The efficient in‐situ reduction and cyclization reaction of aromatic aldehyde, 1,3‐cyclopentanedione (tetronic acid), and nitro‐compound under SnCl2·2H2O‐THF medium

An efficient in‐situ reduction and cyclization reaction for the synthesis of pyrazolo[4,3‐f]quinoline, pyrazolo[3,4‐f]quinoline, and pyrazolo[3,2‐f]quinoline derivatives directly form 5‐nitroindazole, 6‐nitroindazole and 5‐nitroindole in the presence of SnCl₂·2H₂O was reported. Compared to traditional synthetic methods, this approach has the advantages of stable reagents, easy obtaining raw material, and high yields. In this research, SnCl₂·2H₂O is the efficient reducing agent for the in‐situ reduction and cyclization reaction of nitro‐compound. In addition, this process provided an alternative approach for the synthesis of target compounds.