4-Desoxypicropodophyllin and 4’-Demethyl-4-desoxypicropodophyllin Obtained from System (CH_3)_3SiCl/NaI/MeCN

文献报道鬼臼脂素在 (CH3)3SiCl/Nal/MeCN 反应体系中得到氧化产物4-去氧-C环芳构化鬼臼脂素。而本文作者采用a-不饱和苦鬼臼脂素在同样的反应体系中却得到了部分还原产物C环氧化鬼臼脂素。根据鬼臼脂素和苦鬼臼脂素的结构差异,作者对发生这一现象的原因进行了报道和分析。

Biosynthesis of copper nanoparticles supported on manganese dioxide nanoparticles using Centella asiatica L. leaf extract for the efficient catalytic reduction of organic dyes and nitroarenes

In this study we designed a novel,cost‐efficient and green method for the synthesis of copper nanoparticles(Cu NPs)supported on manganese dioxide(MnO2)NPs,using Centella asiatica L.leaf extract as a naturally‐sourced reducing agent,without stabilizers or surfactants.This synthetic process is environmentally‐friendly and avoids the use of toxic reducing agents.Phenolic hydroxyl groups in the leaf extract are believed to reduce Cu2+in solution to generate Cu NPs that are subsequently stabilized on the MnO2NP surfaces.The resulting Cu/MnO2nanocomposite was fully characterized using X‐ray diffraction,transmission electron microscopy,field emission scanning electron microscopy,energy‐dispersive X‐ray spectroscopy and Fourier transform infrared spectroscopy.This material was found to function as a highly active,efficient and recyclable heterogeneous catalyst for the reduction of Congo red,rhodamine B and methylene blue as well as nitro compounds such as2,4‐dinitrophenylhydrazine and4‐nitrophenol in the presence of NaBH4in aqueous media at ambient temperature.The high stability of the Cu/MnO2nanocomposite also allows the catalyst to be separated and reused several times without any significant loss of activity.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Production of Chiral Aromatic Alcohol by Asymmetric Reduction with Vegetable Catalyst

Chiral aromatic alcohols are the key chiral building block for many important enantiopure pharmaceu-ticals. In this work,we studied asymmetric reduction of prochiral aromatic ketone to produce the corresponding chiral alcohol using vegetables as the biocatalyst. Acetophenone was chosen as the model substrate. The results in-dicate that acetophenone can be reduced to the corresponding chiral alcohols with high enantioselectivity by the chosen vegetables,i.e. apple(Malus pumila),carrot(Daucus carota),cucumber(Cucumis sativus),onion(Allium cepa),potato(Soanum tuberosum),radish(Raphanus sativus),and sweet potato(Ipomoea batatas) . In the reaction,R-1-phenylethanol is produced with apple,sweet potato and potato as the catalyst,while S-1-phenylethanol is the product with the other vegetables as the catalyst. In term of the enantioselectivity and reaction yield,carrot(D. ca-rota) is the best catalyst for this reaction. Furthermore,the reaction characteristics were studied in detail using car-rot(D. carota) as the biocatalyst. The effects of various factors on the reaction were investigated and the optimal reaction conditions were determined. Under the optimal reaction conditions(reaction time 50 h,substrate concen-tration 20 mmol·L-1,reaction temperature 35 °C and pH 7),95% of e.e.(to S-1-phenylethanol) and 85% chemical yield can be obtained. This work extends the biocatalyst for the asymmetric reduction reaction of prochiral aromatic ketones,and provides a novel potential route to produce enantiopure aromatic alcohols.

Characterization of Basic Nitrogen Aromatic Species Obtained during Fluid Catalytic Cracking by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

The basic-nitrogen aromatic compounds in feedstocks and liquid products from the micro-reactor and soluble components of coke obtained during fluid catalytic cracking （FCC） process were analyzed by the micro-electrospray ioniza- tion （ESI） 9.4T Fourier transform ion cyclotron resonance mass spectrometry （FT-ICR MS） with an average mass resolving power of 300 000 at a mass range of 100--1 200. The analytical results revealed that the coker gas oil （CGO） contained a higher abundance of basic-nitrogen aromatic compounds with the type of-SN to -9N compared with those in deasphalted oil （DAO） and mixed FCC feedstock. After catalytic cracking, the abundance of lowly condensed basic-nitrogen aromatic compounds was much less than those of highly condensed aromatics in the liquid products, with the carbon number mainly ranging from 6 to 25 and the average carbon number of the side-chains equating to 1--5. On the contrary, with respect to the soluble components of coke, the abundance of lowly condensed basic-nitrogen aromatic compounds was more than those of highly condensed aromatics, and the carbon number ranged from 12 to 30, which was much smaller than that of the mixed FCC feedstock but slightly larger than that of the cracked liquid products. These results have provided some fundamental information on FCC process.

A 200-Year Record of Polycyclic Aromatic Hydrocarbons Contamination in an Ombrotrophic Peatland in Great Hinggan Mountain, Northeast China

Peat bogs are regarded as one of the faithful archives of atmospheric polycyclic aromatic hydrocarbons(PAHs) deposition, and a large number of studies on PAHs accumulation in peatlands have been reported in Europe and North America. Comparatively little information is available on peat chronological records of atmospheric PAHs flux in China. We investigated the concentrations and historical accumulation rates of PAHs(AR PAHs) through geochemical analysis of three 210Pb-dated ombrotrophic peat cores from Great Hinggan Mountain, northeast China. Eight USEPA priority PAHs were detected and they are naphthalene(Nap), acenaphthylene(Acl), acenaphthene(Ace), fluorence(Flu), phenanthrene(Phe), anthracene(Ant), fluoranthene(Fla) and pyrene(Pyr), respectively. The average total eight PAHs(tPAHs) concentrations are 135.98- 262.43 μg kg-1 and the average AR tPAHs over the last two centuries are 96.45- 135.98 μg m-2 yr-1. The Ace, Acl and Phe account for 30.93- 54.04%, 25.29- 35.81%, and 9.14- 19.84% of the tPAHs, respectively, and have significant positive correlations with the tPAH. As a result, they are regarded as the iconic compounds of PAHs pollution in this area. A ca.200-yr atmospheric PAHs contamination history was reconstructed from the temporal sequences of bothconcentration and AR tPAHs, suggesting the variation of local environmental pollution. The main sources of the PAHs are identified by two isomer ratios as petrogenic origin including oil extraction and refining process as well as their combustions for industrial development. In addition, the contribution of coal combustion for industrial activities and resident heating could not be ignored. But prior to 1860, the undeveloped industry and most of agricultural activities might mainly account for the low level of PAHs, although it could infer a long-range input of atmospheric PAHs from other industrial areas. Therefore, there is a global implication to study longterm PAHs pollution records and all the results will provide practical significance in formulating policies to achieve sustainable and healthy development.

Photo-induced reductive cross-coupling of aldehydes, ketones and imines with electron-deficient arenes to construct aryl substituted alcohols and amines

Umpolung reactions of C=X bonds(X=O,N)are valuable ways of constructing new C–C bonds,which are sometimes difficult to be constructed using traditional synthetic pathways.Classical polarity inversion of C=X bonds(X=O,N)usually requires air or moisture‐sensitive and strong reducing agents,which limit the feasibility of substrate scope.Herein we describe a photo‐induced reductive cross‐coupling reaction of aldehydes,ketones and imines with electron‐deficient arenes(aromatic nitriles)using fac‐Ir(ppy)3as a photocatalyst and diisopropylethylamine(DIPEA)as a terminal reductant under visible light irradiation.Mild conditions and high yields mean that this new polarity inversion strategy can be used with aryl‐substituted alcohols and amines.Spectroscopic studies and control experiments have demonstrated the oxidative quenching of Ir(ppy)3*by electron‐deficient arenes involved in the key step for the C–C bond formation.

Polycyclic Aromatic Hydrocarbons in Nigerian Oil-based Drill-cuttings： Evidence of Petrogenic and Pyrogenic Effects

Compositional distribution and sources of polycyclic aromatic hydrocarbons （PAHs） in Nigerian oil-based drill-cuttings have been studied for evidence of petrogenic and/or pyrogenic effects with recommendations for the strict enforcement of the ban on the use of oil-based mud in drilling by government regulatory agencies and prior bio-treatment of the drill cuttings before final fate. A 4000 g mass of the drill cuttings obtained from a mud-pit close to a just-completed crude-oil well in the Niger Delta of Nigeria, 920 g of top-soil, which served as microbes and nutrients carrier and 154g of saw dust and poultry droppings were homogenized in a 10-litre plastic container of very low thermal conductivity. The mix ratio of cuttings to top-soil to saw-dust and poultry＇ droppings was 26：6：1. Mixing and watering of the reactors were done at 3 days interval under ambient temperature of 30 ℃ for 42 days. GC-FID results showed that the total initial PAHs concentration of the drill-cuttings was 223.52 mg/kg while the initial individual PAHs concentrations ranged from 1.67 to 70.7 mg/kg, dry weight, with a 90% predominance of the combustion-specific 3-mng PAHs. The ratio of anthracene to （phenanthrene ＋ anthracene） = 0.31 was found to be greater than the 0.10 source-criterion for PAHs fraction of molar-mass 178 g/mol while the ratio of fluoranthene to （pyrene ＋ fluoranthene） = 0.40 was found to be less than the 0.50 source-criterion for fraction of molar-mass 202 g/mol suggesting that the PAHs were from pyrogenic and petrogenic sources. Pyrogenic PAHs might be from a possible local heat effect while petrogenic PAHs might be from anthropogenic petroleum fractions in proprietary oil-based mud used in drilling. However, after bioremediation by composting, the total PAHs remaining in the drill cuttings were 4.25 mg/kg （representing a 98.1% reduction）. The half-lives of the PAHs in the medium ranged from 8 to 43 days.

Phytoremediation of PAH-Contaminated Sediments by Potamogeton Crispus L. with Four Plant Densities

In order to investigate the effect of plant density ofPotamogeton crispus L. on the remediation of sedi- ments contaminated by polycyclic aromatic hydrocarbons, a 54-day experiment with four plant densities （642, 1 604, 2 567 and 3 530 plants/m^2） was conducted. The results showed higher plant density with slower plant growth rate. Surface area per plant was the most sensitive root parameter to plant density. At the end of the 54-day experi- ment, planting P. crispus enhanced the dissipation ratios of phenanthrene and pyrene in sediments by 6.5%-26,2% and 0.95%-13.6%, respectively. The dissipation increment increased with increasing plant density. Plant uptake accounted for only a small portion of the dissipation increments. Furthermore, P. crispus could evidently improve sediment redox potentials, and strong positive correlations between root surface area and the redox potential as well as between the redox potentials and the dissipation ratios of phenanthrene and pyrene were obtained, indicating that the oxygen released by the roots ofP. crispus might be the main mechanism by which P. crispus enhanced the dis- sipation of PAHs in sediments.

Batch washing of saturated hydrocarbons and polycyclic aromatic hydrocarbons from crude oil contaminated soils using bio-surfactant

Desorption of total saturated fractions(i.e. SAT, defined for this study as the summation of the concentrations of the saturated hydrocarbon from n-C10 to n-C26) and polycyclic aromatic fractions(i.e. PAH, defined as the summation of the concentrations of all polycyclic aromatic fractions including the 16 EPA priority PAH) in two types of soils subjected to the changes of p H and salinity and different bio-surfactant concentrations were investigated. In general, compared with the experiments without bio-surfactant addition, adding rhamnolipid to crude oil-water systems at concentrations above its critical micelle concentration(CMC) values benefits SAT and PAH desorption. The results indicate that the change of p H could have distinct effects on rhamnolipid performance concerning its own micelle structure and soil properties. For loam soil, the adsorption of non-aqueous phase liquid(NAPL) and rhamnolipid would be the principle limiting factors during the NAPL removal procedure. For sand soil, less amount of rhamnolipid is adsorbed onto soil. Thus, with the increase of salinity, the solubilization and desorption of rhamnolipid solution are more significant. In summary, the p H and salt sensitivity of the bio-surfactant will vary according to the specific structure of the surfactant characteristics and soil properties.

Quantitative Analysis Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Correlation between Mass Spectrometry Data and Sulfur Content of Crude Oils

Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR MS) has become a powerful tool for analyzing the detailed composition of petroleum samples. However, the correlation between the numerous peaks obtained by FT-ICR MS and bulk properties of petroleum samples is still a challenge. In this study, the internal standard method was applied for the quantitative analysis of four straight-run vacuum gas oils(VGO) by atmospheric pressure photoionization(APPI) FT-ICR MS. The heteroatom class distribution of these VGO samples turned to be different when the concentration changed. Linear relationship between the normalized abundance and the concentration of VGO samples was identified for the total aromatic compounds, aromatic hydrocarbons, S1 and N1 species. The differences of the response factors were also discussed. The sulfur contents of a series of crude oils were proved to be linear with the FT-ICR MS data calibrated by the response factor of S1 species. This study demonstrated the feasibility of the internal standard method in quantitative analysis with APPI FT-ICR MS, and the bulk properties of petroleum samples could be correlated directly with the FT-ICR MS data.

31~P NMR Studies on Quasi-Aromaticity of Mo_3S_3 Core and Structure of {Mo_3(μ_3-S)_3[μ-SOP(OEt)_2][S_2P(OEt)_2]_3(CH3CN)}*CH_3CN

The title compound {Mo3 (μ3,-S) (μ-S)3 [μ-SOP (OEt )2] [S2P (OEt)2]3(CH3CN) }. CH3CN, C20H46,Mo3N2O9P4S11, Mr= 1222. 9, has been synthesized bythe reaction of [Mo3 (μ3,-S) (μ-S)3]4+ with Hdtp (hydrogen diethyldithiophosphate)and its structures was dctermined by X-ray crystallography. The crystal data for the title compound: triclinic, P1, Z= 2, a= 13. 011 (8), b= 13. 411 (9), c= 14. 385 (5)A, a=76. 59(5), B=78. 09(5), Y=82. 20(3), V= 2382(2) A3, Dc= 1.705 g/cm3, μ (MoKa) = 1. 434 mm-1, F (000) = 1228. The structure was refined to R =0.080 for 5485 observed reflections. Quasi-aromaticity in the puckered-ring of Mo3S3was experimentally probed by 31p NMR spectroscopic measurements. The 31p chemicalshifts of ligand DTP’s (diethyldithiophosphate) were modulated by the substituent effect of the adjacent bridging aromatic carboxylate through the long-distance super-conjugation via the trinuclear Mo cluster core.

雪域沉思(外二首)

生活就该这样子吗忧思的泪水爬过暗夜的脸庞汇聚在我的耳朵万籁俱寂 却分明听到白驹所拉的时光之车在雪夜狂奔轰隆隆

Triazine COF-supported single-atom catalyst (Pd/trzn-COF) for CO oxidation

Single-atom catalysts(SACs) with well-defined and specific single-atom dispersion on supports offer great potential for achieving both high catalytic activity and selectivity. Covalent organic frameworks(COFs) with tailormade crystalline structures and designable atomic composition is a class of promising supports for SACs. Herein, we have studied the binding sites and stability of Pd single atoms(SAs)dispersed on triazine COF(Pd1/trzn-COF) and the reaction mechanism of CO oxidation using the density functional theory(DFT). By evaluating different adsorption sites, including the nucleophilic sp2C atoms, heteroatoms and the conjugated π-electrons of aromatic ring and triazine, it is found that Pd SAs can stably combine with trzn-COF with a binding energy around-5.0 eV, and there are two co-existing dynamic Pd1/trzn-COFs due to the adjacent binding sites on trzn-COF. The reaction activities of CO oxidation on Pd1/trzn-COF can be regulated by the anion–π interaction between a +δ phenyl center and the related-δ moieties as well as the electron-withdrawing feature of imine in the specific complexes. The Pd1/trzn-COF catalyst is found to have a high catalytic activity for CO oxidation via a plausible tri-molecular Eley-Rideal(TER) reaction mechanism. This work provides insights into the d–π interaction between Pd SAs and trznCOF, and helps to better understand and design new SACs supported on COF nanomaterials.

Sources and distribution of polycyclic aromatic hydrocarbons of different glaciers over the Tibetan Plateau

Twenty snow samples were collected from the Qiyi glacier in Qilian Mountains,the Yuzhufeng glacier in eastern Kunlun Mountains,the Xiaodongkemadi glacier in Tanggula Mountains,and the Gurenhekou glacier in Nyainqêntanglha Range over the Tibetan Plateau.The concentration and distribution features of sixteen priority Polycyclic Aromatic Hydrocarbons (PAHs) were determined by gas chromatography equipped with a mass spectrometry detector (GC-MS).The sources of these PAHs were explored as well.Our results indicated that the average concentrations of PAHs in snow were in the range of 20.45 60.57 ng/L.Maximum PAHs levels were found in the YZF glacier andminimum in the XDKMD glacier.However,no apparent regional distribution pattern of PAHs was found in the glaciers over the Tibetan Plateau.Moreover,the 2 4 ring low molecular weight PAHs predominated in snow samples and the concentrations of phenanthrene was the highest.Integrated factor analysis and isomer pair ratios suggested that PAHs of glaciers over the Tibetan Plateau were derived from low temperature combustion of coal and biomass,and partially from the exhaust gas of locomotives.Air mass back trajectory indicated that organic compounds detected in snowpit of these four glaciers,in the period of time they represented,mainly came from Central Asia and the arid area of Northwest China by westerly wind circulation.

The thiamine-dependent enzyme of the vitamin K biosynthesis catalyzes reductive C-N bond ligation between nitroarenes and α-ketoacids

The thiamine-dependent enzyme （1R, 2S, 5S, 6S）-2-succinyl-5-enolpyruvyl-6-hydroxyl-3-cyclohexene-l-carboxylate （SEPHCHC） synthase, also known as MenD, catalyzes a Stetter-like reaction in the biosynthesis of vitamin K. It is found to catalyze a novel reductive C-N bond ligation reaction between nitroarenes and et-ketoacids to form N-hydroxamates. This reaction likely pro- ceeds through an enzyme-mediated, slow two-electron reduction of the nitroalkanes to form a nitroso intermediate, which serves as the electrophilic acceptor of the ketoacid-derived acyl anion. The involvement of the nitroso intermediate is support- ed by the fact that similar N-hydroxamates are readily formed at a much higher rate when nitroso compounds replace the nitro substrates in the chemoenzymatic reactions. These results demonstrate that the thiamine-dependent enzyme is able to catalyze novel, nonnative reactions that may find new chemoenzymatic applications.

Redox-triggered hydroarylation of o-(hydroxyalkyl)arylalkynes with arylsulfonyl chlorides using visible light catalysis

A new radical-mediated method for the synthesis of 1-(2-(1,2-diarylvinyl)phenyl)ethan-1-ones by the redox hydroarylation of o-(hydroxyalkyl)arylalkynes with arylsulfonyl chlorides is described. This visible light catalysis method proceeds via a sequence of the radical addition of aryl group across the C?C triple bond, protonation and redox reaction, and represents a new redox transformation reaction directed by a neighboring hydroxyl group.

FeCl_3·6H_2O-catalyzed selective reduction of allylic halides to alkenes with concomitant oxidation of benzylic alcohols to aldehydes

Iron-catalyzed direct reduction of allylic halides with benzylic alcohol was achieved,providing a new,simple,and efficient method for conducting highly regioselective hydrodehalogenation.This method not only features a readily available reductant,an inexpensive catalyst,simple manipulation,and good tolerance of functional groups including nitriles,nitro,esters,and methoxyl groups,it also has mild reaction conditions and shows complete regioselectivity in that only halides sited at the allylic position are reduced.Alternatively,this method can be applied in the selective transformation of benzylic alcohols to aromatic aldehydes without overoxidation to carboxylic acids.