Separation and Analysis of Oxygen-Containing Compounds in a Shaanxi Middle/Low-Temperature Coal Tar.

A middle/low-temperature coal tar (M/LTCT) was obtained from a low-temperature carbonization plant in Shaanxi, China. The M/LTCT was separated into light components and coal tar pitch through extraction. A series of alkanes, aromatic hydrocarbons, oxygen-containing arenes (OCAs), and nitrogen-containing arenes were fractionated from light components by medium-pressure preparative chromatography with gradient elution using petroleum ether and ethyl acetate. They were analyzed using a gas chromatography-mass spectrometer (GC-MS) and a Fourier transform infrared spectrometer. The OCAs were analyzed by a Fourier transform Orbitrap MS (quadrupole exactive Orbitrap mass spectrometer), and the molecular distribution of the O 1-O 6 species was studied. OCAs are mainly oxygen-containing aromatic compounds, including aromatic phenols, furans, alkoxy aromatic hydrocarbons, aromatic ethers, aromatic aldehydes, aromatic ketones, and aromatic acids. The position of the oxygen atom on the aromatic ring and the condensation form of the aromatic ring are studied.

N/O Co-doped Porous Carbons Derived from Coal Tar Pitch for Ultra-high Specific Capacitance Supercapacitors.

In this paper, a series of N/O co-doped porous carbons (PCs) were designed and used to prepare coal tar pitch-based supercapacitors (SCs). The introduction of N/O species under the intervention of urea effectively improves the pseudocapacitance of PCs. The results show that the specific surface area of synthesized N3PC4-700 is 1914 m2 g-1, while the N and O contents are 1.3 and 7.2%, respectively. The unique interconnected pore structure and proper organic N/O co-doping, especially the introduction of pyridine-N and pyrrole-N, are beneficial for improving the electrochemical performance of PCs. In the three-electrode system, the specific capacitance and rate capability of N3PC4-700 are 532.5 F g-1 and 72.5% at the current densities of 0.5 and 20 A g-1, respectively. In addition, the specific capacitance of N3PC4-700 in a coin-type symmetric device is 315.5 F g-1 at 0.5 A g-1. The N3PC4-700 electrode provides an energy density of 43.8 W h kg-1 with a power density of 0.5 kW kg-1 and still maintains a value of 29.7 at 10 kW kg-1. After 10,000 charge/discharge cycles, the retention rate was as high as 96.7%. In order to obtain high-performance carbon-based SCs, the effective identification and regulation of organic N/O species is necessary.

Detoxification modification of coal-tar pitch by ultraviolet & microwave radiation-enhanced chemical reaction and toxicity evaluation by chemical index and cytotoxicity assay in vitro.

Although coal tar pitch (CTP) has a large yield in China, its large-scale and effective utilization is significantly hindered because of existing and possibly releasing polycyclic aromatic hydrocarbons (PAHs). Therefore, it is an imminent problem how to prepare an environmentally friendly CTP by detoxification modification. In the investigation, a typical CTP was subjected to structural characterization via solid-state 13C NMR and gas chromatograph/mass spectrometer, which confirmed the existence of dominant PAHs such as fluoranthene, pyrene, as well as benzo[a]pyrene, and few heterocyclic compounds. Subsequently, the CTP was modified using 10-undecenal via alkylation reaction enhanced by ultraviolet & microwave radiation. Compared with the original CTP, the total content of 16 toxic PAHs in the modified CTP decreased with a reduction efficiency of above 90%. According to different environmental standards, toxic equivalent quotient of CTP after modification was reduced by above 90%. In order to veritably and fully evaluate the toxicity of CTP, a living vascular smooth muscle cell (A-10 cell) in vitro was used in the cell counting kit-8 assay. The viability of A-10 cell was always higher when exposed to modified CTP than the original CTP. These results powerfully indicated that the enhanced modification was actually effective and efficient for reducing the toxicity of CTP.

Sequential thermal dissolution of two low-rank coals and characterization of their structures by high-performance liquid chromatography/time-of-flight mass spectrometry and gas chromatography/mass spectrometry.

RATIONALE: Gas chromatography/mass spectrometry (GC/MS) and high-performance liquid chromatography/time-of-flight mass spectrometry (HPLC/TOF-MS) were used to separate and reveal the molecular characteristics of organic matter in low-rank coals. METHODS: Six soluble portions (SPs) were obtained by sequential thermal dissolution (TD) of two low-rank coals in the order of cyclohexane, acetone and methanol solvents at 300°C. Organic matter with different molecular characteristics were enriched in eachTD extract, which was further separated and analyzed by GC/MS and HPLC/TOF-MS using an electrospray ionization source in positive mode to obtain a comprehensive understanding of the structural composition of coals. RESULTS: Low polarity compounds like alkanes and arenes have a better solubility in cyclohexane. Phorone has the highest relative abundance in the acetone SPs, and the main compounds detected in the methanol SPs are alcohols and phenols. According to the data from HPLC/TOF-MS, most of the oxygen atoms are in the form of carbonyl and alkoxy groups. The nitrogen-containing compounds in SPs are mainly saturated aliphatic amines and pyridines. The sulfur-containing compounds mainly exist in the form of thioalkanes and thiophenes. CONCLUSIONS: Non-destructive methods were used to obtain soluble matter from coals, and different chromatographic and mass spectrometric techniques were used to separate and analyze the organic matter in coals. Detailed molecular structural information was obtained for the efficient and clean utilization of low-rank coals.

Preparation of layered-porous carbon from coal tar pitch narrow fractions by single-solvent extraction for superior cycling stability electric double layer capacitor application.

Coal tar pitch (CTP) with high carbon content and wide source of raw materials was an excellent precursor for the preparation of porous carbons (PCs). CTP was composed of polycyclic aromatic hydrocarbons (PAHs) with complex molecular size and chemical structure, the separation of CTP into several fractions with relatively narrow molecular weight by solvent extraction was of significance for CTP utilization. In this paper, CTP was treated by single-solvent extraction (carbon disulfide, acetone and ethyl acetate), and the six fractions were used as raw materials to prepare PCs as electrode material for electric double layer capacitor. The fractions were well characterized and the effect of mass distribution of different narrow fractions on structure property and electrochemical performance of the PCs was studied. The PCs prepared by carbon disulfide extract, acetone raffinate and ethyl acetate extract, containing more PAHs, exhibited the excellent specific capacitance performance in comparison with its residual components. The remarkable performance might contribute in the enhanced transport of electrolyte ions via the molecular graphene structure of PAHs. Additionally, the PC prepared by carbon disulfide raffinate showed outstanding cycling performance (99.7% at 2 A g-1 after 15,000 cycles) which was related to its unique layered porous structure.

N/O co-doped porous interconnected carbon nanosheets from the co-hydrothermal treatment of soybean stalk and nickel nitrate for high-performance supercapacitors.

Porous interconnected carbon nanosheets (PICNs) with high electrochemical performance were prepared by doping urea and a co-hydrothermal precursor derived from soybean stalk (SS) and nickel nitrate. The specific surface area and average pore diameter of the as-synthesized PICNs are 2226.29 m2 g-1 and 1.89 nm, and their N and O contents are 5.08% and 9.4%, respectively, which is beneficial for increasing pseudocapacitance. Furthermore, the doping of the metal Ni increases the graphitization degree of the PICNs and promotes the conversion of pyridine-N to graphitized-N. Therefore, the PICNs possess a high specific capacitance of 407 F g-1 at a current density of 0.5 A g-1, a high capacitance retention of 78.62% even at 20 A g-1, and an outstanding cycling stability (over 93% retention rate after 10,000 charge/discharge cycles). Moreover, an energy density of 36.11 W h kg-1 is achieved at a power density of 517.8 W kg-1 during a two-electrode system test, and a retention rate of 87.5% is obtained after 10,000 cycles. This co-hydrothermal treatment as well as nitrogen-doping approach for preparing porous interconnected carbon from SS not only represents an alternative strategy for carbon-based supercapacitor materials but also provides a new option for the utilization of waste SS.

Selective and effective separation of five condensed arenes from a high-temperature coal tar by extraction combined with high pressure preparative chromatography.

An environmentally benign and cost-effective method was designed for isolating and purifying condensed arenes from acetone-extractable portion (AEP) of a high-temperature coal tar through a high pressure preparative chromatograph (HPPC) with different packings, including silica gel, octadecyl silane, octyl bonded silica gel, and diol bonded silica gel. In total, 196 compounds were detected with a gas chromatograph/mass spectrometer from AEP and its eluates. From the eluates, naphthalene, anthracene, phenanthrene, fluoranthene, and pyrene were successfully isolated and purified, and their structures were confirmed by their 1H and 13C nuclear magnetic resonance spectra in addition to their mass spectra. Extraction-HPPC device and solvent recovery process were designed and developed, which can potentially be applied to industrial production because the process is easy-to-operate and ecofriendliness. In addition, the solvents used can be easily recovered and reused, and neither waste water nor other pollutions are emitted.

Enhancement of light aromatics from catalytic fast pyrolysis of cellulose over bifunctional hierarchical HZSM-5 modified by hydrogen fluoride and nickel/hydrogen fluoride.

Pore structure and accessible active sites of HZSM-5 (Z5) are the key factors for its catalysis. The bifunctional hierarchical Z5 were prepared with leaching agent HF and loading Ni, and their performance for catalytic fast pyrolysis (CFP) of cellulose was investigated in a drop tube quartz reactor. Z5 modified with 0.5 mol/L HF (0.5F-Z5) showed excellent light aromatics (LAs) yield, which can be attributed to the enhancement in the small mesopores (2-10 nm) and the decrease of Brønsted acid sites during dealumination. Simultaneously, the loading of a 1 wt% Ni produced more LAs than 0.5F-Z5, due to the improvement in deoxidation/hydrogenation reactions. The highest LAs yield (31.3%) was obtained over 1%Ni-0.5 mol/LHF-Z5, which increased by 44.9% compared to the parent Z5. In addition, the reaction routes over different active centers and acid-catalyzed reactions were analyzed, based upon the composition of bio-oils and catalyst characterization.

Optimization of Ultrasonic-Microwave Assisted Extraction and Hepatoprotective Activities of Polysaccharides from Trametes orientalis.

Ultrasonic-microwave assisted extraction (UMAE) of Trametes orientalis polysaccharides was optimized by response surface methodology. Hepatoprotective effects of a purified T. orientalis polysaccharide (TOP-2) were evaluated by alcohol-induced liver injury model mice. The optimal UMAE parameters were indicated as below: ratio of water to raw material 28 mL/g, microwave power 114 W, extraction time 11 min. The polysaccharides yield was 7.52 ± 0.12%, which was well consistent with the predicted value of 7.54%. Pre-treatment with TOP-2 effectively increased the liver index and spleen index in alcohol-treated mice. The elevated serum alanine aminotransferase (ALT) and aspartate aminotransferase (AST) levels of mice after alcohol exposure were inhibited by TOP-2 administration. The liver tumor necrosis factor-α (TNF-α), interleukin-1ß (IL-1ß) levels have decreased significantly as a result of alcohol exposure, while pre-treatment with TOP-2 could mitigate these consequences. Furthermore, pre-treatment with TOP-2 could efficiently boost the superoxidase dismutase (SOD), catalase (CAT) and glutathione peroxidase (GSH-Px) activities, and observably constrain the malondialdehyde (MDA) level. The findings suggest that TOP-2 might be useful for alleviating the alcohol-induced hepatotoxicity via its antioxidant and anti-inflammatory potential.

Ameliorative effect of Trametes orientalis polysaccharide against immunosuppression and oxidative stress in cyclophosphamide-treated mice.

The present study evaluated the ameliorative effects of Trametes orientalis polysaccharide (TOP-2) against cyclophosphamide (CP) induced toxicity in mice. Intraperitoneal administration of TOP-2 not only effectively increased the thymus, spleen, heart, liver, and kidney indices, but also significantly enhanced the phagocytic activities of macrophages and splenocyte proliferation, dose-dependently. The lowered nitric oxide level of macrophages after CP treatment was elevated by TOP-2 administration. Impaired splenic natural killer cells and cytotoxic T lymphocytes activities were remarkably enhanced by TOP-2. Furthermore, the levels of interleukin-2, interferon-γ, Immunoglobulin A, immunoglobulin G, and immunoglobulin M were notably reduced by CP, while TOP-2 abolished these effects. TOP-2 could also effectively increase the total antioxidant capacity, superoxidase dismutase, catalase and glutathione peroxidase activities, and inhibit the increase in malondialdehyde level. These results indicate that TOP-2 may be of therapeutic value in ameliorating the immunosuppression and oxidative stress caused by CP treatment, through its immunomodulatory and antioxidant potential.

Characterization of a bio-oil from pyrolysis of rice husk by detailed compositional analysis and structural investigation of lignin.

Detailed compositional analysis of a bio-oil (BO) from pyrolysis of rice husk was carried out. The BO was extracted sequentially with n-hexane, CCl(4), CS(2), benzene and CH(2)Cl(2). In total, 167 organic species were identified with GC/MS in the extracts and classified into alkanes, alcohols, hydroxybenzenes, alkoxybenzenes, dioxolanes, aldehydes, ketones, carboxylic acids, esters, nitrogen-containing organic compounds and other species. The benzene ring-containing species (BRCCs) were attributed to the degradation of lignin while most of the rests were derived from the degradation of cellulose and hemicellulose. Along with guaiacyl and p-hydroxyphenyl units as the main components, a new type of linkage was suggested, i.e., C(ar)-CH(2)-C(ar) in 4,4'-methylenebis(2,6-dimethoxyphenol). Based on the species identified, a possible macromolecular structure of the lignin and the mechanism for its pyrolysis are proposed. The BO was also extracted with petroleum ether in ca. 17.8% of the extract yield and about 82.1% of the extracted components are BRCCs.

Fractionation and identification of organic nitrogen species from bio-oil produced by fast pyrolysis of sewage sludge.

Pyrolysis of sewage sludge was performed at 500 degrees C and a sweeping gas flow rate of 300 cm(3)/min in a drop tube furnace. Liquid fraction (i.e., bio-oil) from the sewage sludge pyrolysis was separated by silica-gel column chromatography (SGCC) with different solvents, including mixed solvents, as eluants. A series of alkanenitriles (C(13)-C(18)), oleamide, alkenenitrile, fatty acid amides and aromatic nitrogen species were fractionated from the bio-oil by SGCC and analyzed with a gas chromatography/mass spectrometry (GC/MS). Most of the GC/MS-detectable organic nitrogen species (ONSs) are lactams, amides and N-heterocyclic compounds, among which acetamide is the most abundant. N-heterocyclics with 1-3 rings, including pyrrole, pyridine, indole, benzoimidazole, carbazole, norharman and harman, were observed. The lactams detected include pyrrolidin-2-one, succinimide, phathalimide, glutarimide, piperidin-2-one and 3-isobutylhexahydropyrrolo[1,2-a]pyrazine-1,4-dione, all of which should be formed via decarboxylation and cyclization of gamma- and delta-amino acids. Such a procedure provides an effective approach to fractionation and identification of ONSs from bio-oil produced by fast pyrolysis of sewage sludge.

Triacetonamine formation in a bio-oil from fast pyrolysis of sewage sludge using acetone as the absorption solvent.

A sewage sludge sample was pyrolyzed in a drop tube furnace at 500 degrees C and sweeping gas flow rate of 300cm(3)/min. Triacetonamine (TAA) was detected with GC/MS as major component in the resulting bio-oil using acetone as the absorption solvent and proven to be a product from the reaction of NH(3) in the bio-oil with the absorption solvent acetone. TAA yield increased with storage time and reached a level about 28.4% (% sludge fed, daf) after 175h. Since the reaction of pure NH(3) with acetone does not proceed, some species in the bio-oil must catalyze the reaction of NH(3) with acetone. TAA was isolated in a high yield (27.9%, daf) and high purity (80.4%) by column chromatography with different solvents, including mixed solvents, as eluants. The study revealed the possibility of sewage sludge as potential resource of TAA.

Synthesis and antitumor activity of 20-O-linked nitrogen-based camptothecin ester derivatives.

A series of nitrogen-based 20S-hydroxyl camptothecin ester derivatives were prepared. 3-Aminopropionate of camptothecin was found more cytotoxic in vitro on several human tumor cell lines than 3-amidopropionate of camptothecin. Ester 16 showed best antitumor activity in vivo and in vitro in all esters we prepared.