ALBERT

Description: In experimental investigations on axial symmetry, over-ventilated CH 4 /air diffusion combustion in a packed bed is executed to study the height, shape and stability of the flame. The combustor is a quartz tube packed with alumina pellets in which a cylindrical fuel stream is surrounded by a coflow air nozzle. The results show that the bed length and pellet diameter have a significant influence on the flame properties. In general, the flame above the pellet surface has axial symmetry, and its shape and colour are similar to those of a conventional diffusion flame when the bed length is smaller. The colour of the flame front varies with the bed length. The changed colour indicates an increased flame front temperature and that the combustion regime above the bed surface may change from non-premixed combustion to partially premixed combustion or even premixed combustion owing to the mix and dispersion effect in the packed bed. In addition, multiple flame behaviours, such as an inclined flame front, isolated reaction zone and oscillatory motion followed by a pulsating sound with a few hertz in a packed bed, are observed experimentally. The possible reasons for these phenomena are discussed.

Description: Seven new cucurbitane glucosides, hemslepensides J-P ( 1 – 7 ), and two known compounds, 16,25- O -diacetyl-cucurbitane F ( 8 ) and 25- O -acetyl-23,24-dihydrocucurbitacin F ( 9 ), were isolated from the tubers of Hemsleya pengxianensis var. jinfushanensis . The structures of 1 – 7 were elucidated using infrared absorption spectroscopy, nuclear magnetic resonance spectroscopy and high-resolution electrospray ionization mass spectrometry. The treatment of HT29 cells, human colon cancer cells, with compounds 8 and 9 inhibited cell proliferation. Further study demonstrated that compounds 8 and 9 induced F-actin aggregation, G 2 /M phase cell cycle arrest and cell apoptosis in HT29 cells. In summary, the present study enriched the chemical composition research of H. pengxianensis , and suggested that the compounds 8 / 9 treatment may be a potentially useful therapeutic option for colon cancer.

Description: An organic–inorganic hybrid compound with an extensive three-dimensional (3D) crystal structure, (3-nitroanilinium) 2 (18-crown-6) 2 (H 2 PO 4 ) 2 (H 3 PO 4 ) 3 (H 2 O) ( 1 ), was synthesized under slow evaporation conditions. Differential scanning calorimetry measurements indicated that 1 underwent a reversible phase transition at ca 231 K with a hysteresis width of 10 K. Variable-temperature X-ray single-crystal diffraction revealed that the phase transition of 1 can be ascribed to coupling of pendulum-like motions of its nitro group with proton transfer in O–H···O hydrogen bonds of the 3D framework. The temperature dependence of its dielectric permittivity demonstrated a step-like change in the range of 150–280 K with remarkable dielectric anisotropy, making 1 a promising switchable dielectric material. Potential energy calculations further supported the possibility of dynamic motion of the cationic nitro group. Overall, our findings may inspire the development of other switchable dielectric phase transition materials by introducing inorganic anions into organic–inorganic hybrid systems.

Description: To explore metabolism mechanism of paeoniflorin in the liver and further understand intact metabolism process of paeoniflorin, a rapid, convenient and effective assay is described using ultra-performance liquid chromatography coupled with hybrid quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS/MS). The strategy was confirmed in the following primary processes: firstly, different concentration of paeoniflorin, rat liver microsomes, coenzymes and different incubated conditions were optimized to build a biotransformation model of rat liver microsomes in vitro by high performance liquid chromatography with diode array detection (HPLC-DAD); secondly, the metabolites of paeoniflorin in rat liver microsomes were detected and screened using UPLC-Q-TOF-MS/MS by comparing the total ion chromatogram (TIC) of the experimental group with those of control groups; finally, the molecular formulae and corresponding chemical structures of paeoniflorin metabolites were identified by comparing the MS and MS/MS spectra with the self-constructed database and simulation software. Based on this analytical strategy, 20 metabolites of paeoniflorin were found and 6 metabolites (including four new compounds) were tentatively identified. It was shown that hydrolysis and oxidation were the major metabolic pathways of paeoniflorin in rat liver microsomes, and the main metabolic sites were the structures of pinane and the ester bond. These findings were significant for a better understanding of the metabolism of paeoniflorin in rat liver microsomes and the proposed metabolic pathways of paeoniflorin might provide fundamental support for the further research in the pharmacological mechanism of Paeoniae Radix Rubra (PRR).

Description: Types of resins anchored on citric acid were synthesized and identified. The citric acid-modified resins PS-CA, PS-O-CA and PS-N-CA were synthesized by anchoring citric acid on PS-Cl, PS-OH and PS-NH 2 , respectively. The PS-CA, PS-O-CA and PS-N-CA were used to adsorb Fe 3+ , Al 3+ , Cu 2+ , Pb 2+ , Cd 2+ and Hg 2+ . The influences of pH, adsorption time and metal ion concentration on the adsorption capacities of the resins were investigated. After optimization, PS-CA was a good adsorbent to Fe 3+ , Cu 2+ , Pb 2+ and Cd 2+ with q m values of 143.9 mg g –1 , 77.4 mg g –1 , 18.9 mg g –1 and 119.9 mg g –1 , respectively. PS-N-CA was a good adsorbent to Al 3+ and Hg 2+ with q m values of 176.6 mg g –1 and 114.9 mg g –1 , respectively. The adsorption kinetics and adsorption isotherm experiments indicated that the pseudo-first-order rate equation was more appropriate for characterizing the kinetic data and the Langmuir model was more suitable for fitting the equilibrium data. The reusability of the citric acid-modified resins was also evaluated and these resins exhibited considerable reusability.

Description: Gold nanoparticles and carbon nanotubes have attracted substantial attention in recent years for their potential applications in photothermal therapy (PTT) as an emerging breakthrough in cancer treatment. Herein, a hybrid nanomaterial of gold nanostars/multiwalled carbon nanotubes (MWCNTs) was synthesized by two-step reduction via the control of several synthetic conditions such as the reducing agent, pH value, concentration and ratio of reagents. The material shows good biocompatibility and high photothermal conversion efficiency, demonstrating its applicability in PTT. The lack of surfactant in the synthesis process made the hybrid nanomaterial cell-friendly, with no effects on viability in vitro . The MWCNT/gold nanostars hybrid nanomaterial presented 12.4% higher photothermal efficiency than gold nanostars alone and showed a 2.4-fold increase over gold nanospheres based on a heating test under 808 nm laser irradiation. Moreover, the MWCNTs/gold nanostars at low concentration (0.32 nM) exhibited remarkably improved photothermal cancer cell-killing efficacy, which may be attributed to the surface plasmon resonance absorption of the gold nanostars and the combined effects of enhanced coupling between the MWCNTs and gold nanostars. Collectively, these results demonstrate that the MWCNTs/gold nanostars developed herein show prominent photothermal value, and thus may serve as a novel photothermal agent for cancer therapy.

Description: The structure of cucurbit[6]uril (CB[6]), as a fascinating supramolecular receptor, is regarded as ‘indestructible’. Herein, we investigated the hydrolysis of CB[6] catalysed by alkali. Our results showed that CB[6] was easily hydrolysed in 30% NaOH at 160°C within 3 h. Separation and purification of hydrolytic products demonstrated the presence of NH 3 , CO 2 , HCOONa, glycine and hydantoic acid. Based on the studies of the hydrolysis of substances similar to CB[6] including 4,5-dihydroxyethyleneurea, glycoluril and glycoluril dimer, we proposed that a plausible reaction mechanism involved a Cannizzaro reaction, which is supported by HPLC, mass spectrometry data and previous reports. Further studies are dedicated towards a controlled hydrolysis of CB[6], which will provide a new route for direct functionalization of CB[6].

Description: The formation mechanism of pentazolate anion (PZA) is not yet clear. In order to present the possible formation pathways of PZA, the potential energy surfaces of phenylpentazole (PPZ), phenylpentazole radical (PPZ-R), phenylpentazole radical anion (PPZ-RA), PPZ and m -chloroperbenzoic acid ( m -CPBA), p -pentazolylphenolate anion ( p -PZPolA) and m -CPBA, and p -pentazolylphenol ( p -PZPol) and m -CPBA were calculated by the computational electronic structure methods including the hybrid density functional, the double hybrid density functional and the coupled-cluster theories. At the thermodynamic point of view, the cleavages of C–N bonds of PPZ and PPZ-R need to absorb large amounts of heat. Thus, they are not feasible entrance for PZA formation at ambient condition. But excitation of PPZ and deprotonation of PPZ-RA probably happen before cleavage of C–N bond of PPZ at high-energy condition. As to the radical anion mechanism, the high accuracy calculations surveyed that the barrier of PZA formation is probably lower than that of dinitrogen evolution, but the small ionization potential of PPZ-RA gives rise to the unstable ionic pair of sodium PPZ at high temperature. In respect of oxidation mechanism, except for PPZ, the reactions of p -PZPolA and p -PZPol with m -CPBA can form PZA and quinone. The PZA formations have the barriers of about 20 kcal mol –1 which compete with the dinitrogen evolutions. The stabilities of PZA in both solid and gas phases were also studied herein. The proton prefers to transfer to pentazolyl group in the (N 5 ) 6 (H 3 O) 3 (NH 4 ) 4 Cl system which leads to the dissociation of pentazole ring. The ground states of M(N 5 ) 2 (H 2 O) 4 (M = Co, Fe and Mn) are high-spin states. The pentazolyl groups confined by the crystal waters in the coordinate compounds can improve the kinetic stability. As to the reactivity of PZA, it can be persistently oxidized by m -CPBA to oxo-PZA and 1,3-oxo-PZA with the barriers of about 20 kcal mol –1 .

Description: To study puff-by-puff release characteristics of crotonaldehyde in mainstream cigarette smoke under diverse intensive smoking regimens, we designed an RM20H smoking machine with a puff-by-puff smoke collection unit to automatically trap crotonaldehyde in the mainstream cigarette smoke. Using this process, we trapped, puff-by-puff, crotonaldehyde in mainstream smoke generated by different smoking regimens and quantitatively analysed the levels of crotonaldehyde using high-performance liquid chromatography with a modified QuEChERS sample pretreatment method. On the basis of the crotonaldehyde in each puff, we determined crotonaldehyde's puff-by-puff release characteristics. The results showed that crotonaldehyde's puff-by-puff release remained nearly constant for the International Organization for Standardization mode while increased polynomial trend was seen ( n ≥ 6) under the Massachusetts and Health Canada smoking regimens. The equation fit for various regimens was good ( R 2 〉 0.9192). Release characteristics by puff were classified into four categories: (1) first, second and third puffs; (2) fourth and fifth puffs; (3) sixth puff; and (4) seventh and eighth puffs.

Description: The phthalate ester compounds in industrial wastewater, as kinds of environmental toxic organic pollutants, may interfere with the body's endocrine system, resulting in great harm to humans. In this work, the photocatalytic degradation properties of dibutyl phthalate (DBP) were investigated using α-Fe 2 O 3 nanoparticles and H 2 O 2 in aqueous solution system. The optimal parameters and mechanism of degradation were discussed by changing the morphology and usage amount of catalysts, the dosage of H 2 O 2 , pH value and the initial concentration of DBP. Hollow α-Fe 2 O 3 nanoparticles showed the highest degradation efficiency when 30 mg of catalyst and 50 µl of H 2 O 2 were used in the DBP solution with the initial concentration of 13 mg l –1 at pH = 6.5. When the reaction time was 90 min, DBP was degraded 93% for the above optimal parameters. The photocatalytic degradation mechanism of DBP was studied by the gas chromatography–mass spectrometry technique. The result showed that the main degradation intermediates of DBP were ortho -phthalate monobutyl ester, methyl benzoic acid, benzoic acid, benzaldehyde, and heptyl aldehyde when the reaction time was 2 h. DBP and its intermediates were almost completely degraded to CO 2 and H 2 O in 12 h in the α-Fe 2 O 3 / H 2 O 2 /UV system.