A theoretical kinetics study on low-temperature oxidation of n-C4H9 radicals

The low-temperature oxidation mechanism of n?butyl radicals (n-C₄H₉) has been investigated by high level quantum chemical calculations coupled with the Rice–Ramsperger–Kassel–Marcus/Master Equation (RRKM/ME) theory. The potential energy surfaces (PES) were explored at the QCISD(T)/CBS//B3LYP/6-311++G(d,p) level. The temperature- and pressure-dependent rate constants were computed and fitted in modified Arrhenius parameters. The major reaction channels were discussed to more deeply understand the competing relationships between chain branching, chain propagation and termination reactions. The results show that the 1,5 H-shift reaction is more competitive than the 1,6 H-shift and 1,4 H-shift for isomerization reactions of n?butyl peroxy radicals, and the concerted HO₂ elimination channel to form butene becomes more important at high temperatures. Furthermore, based on our calculations, a revised kinetic model was developed to describe n-butane oxidation. Good consistency between model predictions and experimental data was shown. This study enhances our understanding of the combustion mechanism of n-butane and can be used as a reliable reference for mechanistic understanding of larger alkanes.     

Exact Recovery of Stochastic Block Model by Ising Model

In this paper, we study the phase transition property of an Ising model defined on a special random graph—the stochastic block model (SBM). Based on the Ising model, we propose a stochastic estimator to achieve the exact recovery for the SBM. The stochastic algorithm can be transformed into an optimization problem, which includes the special case of maximum likelihood and maximum modularity. Additionally, we give an unbiased convergent estimator for the model parameters of the SBM, which can be computed in constant time. Finally, we use metropolis sampling to realize the stochastic estimator and verify the phase transition phenomenon thfough experiments.     

Coherence and Quantum Phase Transition in Spin Models

Based on quantum renormalization group (QRG) method, we investigated quantum coherence and quantum phase transition (QPT) in XXZ chain and XY chain, respectively. The results show that both the geometric quantum coherence and entropic coherecne can accurately indicate the QPT at critical point after enough iteration steps. Moreover, the increasing anisotropy parameter destroys the coherence in the XXZ chain, while enhances it in the XY chain. In addition, focused on the XXZ chain we analyzed the nonanalytic phenomena and scaling behaviors with different theoretical exponents in detail.

     

Complementary relation between quantum entanglement and entropic uncertainty

Quantum entanglement is regarded as one of the core concepts,which is used to describe the nonclassical correlation between subsystems,and entropic uncertainty relation plays a vital role in quantum precision measurement.It is well known that entanglement of formation can be expressed by von Neumann entropy of subsystems for arbitrary pure states.An interesting question is naturally raised:is there any intrinsic correlation between the entropic uncertainty relation and quantum entanglement?Or if the relation can be applied to estimate the entanglement.In this work,we focus on exploring the complementary relation between quantum entanglement and the entropic uncertainty relation.The results show that there exists an inequality relation between both of them for an arbitrary two-qubit system,and specifically the larger uncertainty will induce the weaker entanglement of the probed system,and vice versa.Besides,we use randomly generated states as illustrations to verify our results.Therefore,we claim that our observations might offer and support the validity of using the entropy uncertainty relation to estimate quantum entanglement.     

Exploratory Purification of Compounds from Aqueous Extracts of <Emphasis Type="Italic">Pinus massoniana</Emphasis> Lamb. by Two-Dimensional Preparative Liquid Chromatography

An off-line orthogonal two-dimensional preparative liquid chromatography method was developed for isolation of high-purity compounds from aqueous extracts of Pinus massoniana Lamb., which has efficient therapeutic properties in recipes of traditional Chinese medicines. A polar-enhanced reversed-phase (RP) column, XAqua C18 was selected for the first-dimensional separation. A HILIC column and a hydrophobic RP column were both explored in the second dimension. The preparation results indicated hydrophilic RP × HILIC mode would provide better separation efficiency for polar complexes, i.e., the second-dimensional separation was finished in less than 30 min and high-purity compounds were obtained. In this work, 16 fractions were collected efficiently in the first dimension with a recovery up to 96%, and six compounds with high purity and enough quantity were identified by NMR and high resolution mass spectrometry, including epicatechin, betuloside, taxifolin-3-O-xyloside, cedrusin-4-O-glucoside, massonianoside C and massonianoside D, and five are glycosides, including flavonoid glycosides, lignanoid glycosides and an arylbutanoid glycoside. Betuloside was first reported in the preparation of Pinus massoniana Lamb. This work demonstrated a flexible strategy of compromise in between time and resolution for selecting solvent and column to enhance preparative efficiency of polar complex systems.     

Magnetic Solid-Phase Extraction and Ionic Liquid Dispersive Liquid–Liquid Microextraction Coupled with High-Performance Liquid Chromatography for the Determination of Hexachlorophene in Cosmetics

An efficient, simple, and fast method based on ionic liquid dispersive liquid–liquid microextraction (IL-DLLME) followed by magnetic solid-phase extraction (MSPE) was developed as a new technique for extracting and purifying hexachlorophene (HCP) in cosmetics prior to high-performance liquid chromatography (HPLC) determination. In this method based on IL-DLLME and MSPE, 1-hexyl-3-methylimidazolium hexafluorophosphate ([C₆MIM][PF₆]) is used as the extraction solvent and Fe₃O₄ nanoparticles are used to remove hydrophobic additives in the cosmetics by physical adsorption. The main parameters affecting the efficiency of the IL-DLLME and MSPE of HCP were investigated and optimized. Under the optimum conditions, the method was linear in the range 0.5–40 µg mL^?1 with a correlation coefficient (R ²) of 0.9976 and had a detection limit of 0.14 µg mL^?1 at a signal-to-noise ratio (S/N) of 3. The recoveries of HCP in three cosmetic samples using the proposed method were in the range 74.5–97.7%, and the relative standard deviations (RSD, n = 5) were in the range 3.8–6.7%. The developed method was successfully applied to the determination of HCP in cosmetics.     

Determination of Enantiomeric Purity of GSK962040 Based on Liquid Chromatography Using Chiral Stationary Phase Combined with a Pre-column Derivatization Procedure

A sensitive and accurate LC method was developed and further validated for the determination of enantiomeric purity of GSK962040. Before separation, a pre-column derivatization procedure was performed. Baseline separation with a resolution higher than 1.9 was accomplished within 15 min using a Chiralpak AD-H (250 × 4.6 mm; particle size 5 μm) column, with n-hexane: 2-propanol (85:15 v/v) as mobile phase at a flow rate of 1 mL min^?1. The eluted analytes were subsequently detected with a UV detector at 260 nm. The effects of mobile phase components and temperature on enantiomeric selectivity as well as resolution of enantiomers were thoroughly investigated. The calibration curves were plotted within the concentration range between 4 and 200 μg mL^?1 (n = 8), and recoveries between 98.15 and 101.48% were obtained, with relative standard deviation (RSD) lower than 1.42%. The LOD and LOQ for the Boc-GSK962040 were 1.23 and 4.15 μg mL^?1 and for its enantiomer were 1.38 and 4.76 μg mL^?1, respectively. The developed method was also evaluated and validated by analyzing bulk samples with different enantiomeric ratios of GSK962040. It was demonstrated that the method was accurate, robust and sensitive, and also had practical utilities for real analysis.     

Core-shell magnetic molecularly imprinted polymer nanoparticles for the extraction of triazophos residues from vegetables

The authors report on a surface molecular imprinting strategy for synthesizing magnetic and molecularly imprinted core-shell polymer nanoparticles (MMIPs) with a typical size of 320 nm. The triazophos-imprinted polymer shell on 180-nm magnetite particles (modified with 3-methacryloxypropyl trimethoxysilane) was obtained by radical polymerization of ethylene glycol dimethacrylate in the presence of triazophos, this followed by extractive removal of triazophos. The resulting MMIPs possess large binding capacity, high recognition selectivity, and fast binding kinetics for triazophos. They can be easily separated from a solution by using a magnet. These features result in a convenient and selective solid-phase extraction procedure for triazophos prior to its determination by UV spectrometry or by GC analysis. The method was successfully applied to the extraction and clean-up of triazophos residues in spiked homogenates of vegetables with recoveries in the range of 89.2 ~ 99.0%. The detection limits for triazophos by the UV assay and GC assay are 0.93 nM and 0.32 nM, respectively.

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Graphical abstract The core-shell magnetic molecularly imprinted polymer nanoparticles (MMIPs) with a nanoscale triazophos-imprinted polymer shell were prepared by surface imprinting onto the surfaces of 3-methacryloxypropyl trimethoxysilane (MATS) modified Fe₃O₄ magnetic nanoparticles. They were successfully applied for the extraction and clean-up of ultra trace triazophos residues in spiked homogenates of vegetable samples. MMIPs exhibit the larger binding capacity, faster binding kinetics, higher recognition selectivity, good reusability and stability, and excellent magnetic responses.

     

DBSA-catalyzed hydrolysis of chain α-oxo ketene dithioacetals in water: Aqueous synthesis of β-ketothioesters

In this paper, we wish to report an environment friendly synthetic method for β-ketothioesters from a dodecylbenzenesulfonic acid (DBSA)-catalyzed hydrolysis reaction of chain α-oxo ketene dithioacetals in water. It was shown that the hydrolysis reaction of chain α-oxo ketene dithioacetals could efficiently occur in the presence of 7.5?mol% DBSA at 100?°C in water, affording the desired β-keto thioesters in excellent yields.     

New biphenantherene and nervogenic acid derivatives from Liparis regnieri Finet and their inhibitory activities against NF-κB activation

A phytochemical investigation of the whole plant of Liparis regnieri Finet led to the isolation of one new biphenantherene (1) and ten new nervogenic acid derivatives (2–11), together with nine known compounds. Their structures were elucidated mainly by extensive analyses of 1D and 2D NMR spectroscopic data and chemical reactions. Additionally, for the first time a previously unreported biphenantherene was discovered to effectively suppress TNF-α induced expression of NF-κB-Luc in Hela cells with the IC₅₀ value of 1.80 μM and the structure-activity relationshipwas also discussed.