Highly selective extraction of aromatics from aliphatics by using metal chloride-based ionic liquids

The separation of aromatics from aliphatics is essential for achieving maximum exploitation of oil resources in the petrochemical industry.In this study,a series of metal chloride-based ionic liquids were prepared and their performances in the separation of 1,2,3,4-tetrahydronaphthalene(tetralin)/dodecane and tetralin/decalin systems were studied.Among these ionic liquids,1-ethyl-3-methylimidazolium tetrachloroferrate([EMIM][FeCl_(4)])with the highest selectivity was used as the extractant.Density functional theory calculations showed that[EMIM][FeCl_(4)]interacted more strongly with tetralin than with dodecane and decalin.Energy decomposition analysis of[EMIM][FeCl_(4)]-tetralin indicated that electrostatics and dispersion played essential roles,and induction cannot be neglected.The van der Waals forces was a main effect in[EMIM][FeCl_(4)]-tetralin by independent gradient model analysis.The tetralin distribution coefficient and selectivity were 0.8 and 110,respectively,with 10%(mol)tetralin in the initial tetralin/dodecane system,and 0.67 and 19.5,respectively,with 10%(mol)tetralin in the initial tetralin/decalin system.The selectivity increased with decreasing alkyl chain length of the extractant.The influence of the extraction temperature,extractant dosage,and initial concentrations of the system components on the separation performance were studied.Recycling experiments showed that the regenerated[EMIM][FeCl_(4)]could be used repeatedly.

Intercalation assisted liquid phase production of disulfide zirconium nanosheets for efficient electrocatalytic dinitrogen reduction to ammonia

Disulfide zirconium(ZrS_(2)) is a two-dimensional(2D) transition metal disulfide and has given rise to extensive attention because of its distinctive electronic structure and properties.However,mass production of high quality of ZrS_(2)nanosheets to realize their practical application remains a challenge.Here,we have successfully exfoliated the bulk ZrS_(2)powder with the thickness of micron into single and few-layer nanosheets through liquid-phase exfoliation in N-methylpyrrolidone(NMP) assisted via aliphatic amines as intercalators.It is found that the exfoliation yield is as high as 27.3%,which is the record value for the exfoliation of ZrS_(2)nanosheets from bulk ZrS_(2)powder,and 77.1% of ZrS_(2)nanosheets are 2-3 layers.The molecular geometric size and aliphatic amine basicity have important impact on the exfoliation.Furthermore,the ZrS_(2)nanosheets have been used as catalyst in the electrocatalytic dinitrogen reduction with the NH3yield of 57.75 μg h^(-1)mg_(cat.)^(-1),which is twice that by ZrS_(2)nanofibers reported in literature and three times that by the bulk ZrS_(2)powder.Therefore,the liquid phase exfoliation strategy reported here has great potential in mass production of ZrS_(2)nanosheets for high activity electrocatalysis.

Aliphatic biomarker signatures of early Oligocene-early Miocene source rocks in the central Qiongdongnan Basin:Source analyses of organic matter

The geochemical signatures of fifty-four rock samples and three supplementary drill stem test(DST)oils from the Yacheng-Sanya formations in the central Qiongdongnan Basin(CQB)were analysed.Reconstruction of the early Oligocene-early Miocene(36–16 Ma)palaeovegetation and source analyses of organic matter(OM)were conducted using aliphatic biomarkers in ancient sediments and DST oils.Both the interpreted aquatic and terrigenous OM contributed to the CQB source rocks(SRs)but had varying relative proportions.The four distribution patterns derived from n-alkanes,terpanes,and steranes are representative of four OM composition models of the Yacheng-Sanya SRs,including model A,model B,model C,and model D,which were classified based on the increasing contribution from terrigenous OM relative to aquatic OM.Some terrigenous higher plantderived biomarkers,including oleanane,des-A-oleanane,C_(29)ααα20R sterane,bicadinanes,the C_(19)/(C_(19)+C_(23))tricyclic terpane ratio,and other n-alkane-derived ratios suggest that angiosperms had increased proportions in the palaeoflora from early Oligocene to early Miocene,and the bloom of terrigenous higher plants was observed during deposition of upper Lingshui Formation to lower Sanya Formation.These findings are consistent with the incremental total organic carbon and free hydrocarbons+potential hydrocarbons(S_1+S_2)in the lower Lingshuilower Sanya strata with a significant enrichment of OM in the E_3l_1-N_1s_2 shales.The maturity-and environmentsensitive aliphatic parameters of the CQB SRs and DST oils suggest that all the samples have predominantly reached their early oil-generation windows but have not exceeded the peak oil windows,except for some immature Sanya Formation shales.In addition,most of the OM in the analysed samples was characterised by mixed OM contributions under anoxic to sub-anoxic conditions.Furthermore,terrestrial-dominant SRs were interpreted to have developed mainly in the Lingshui-Sanya formations and were deposited in sub-oxic to oxic environments,compared to the anoxic to sub-anoxic conditions of the Yacheng Formation.

直接电导检测离子排斥色谱法测定C_1～C_6脂肪族有机酸

建立了直接电导检测离子排斥色谱分离测定C1-C6脂肪族有机酸（甲酸、乙酸、丙酸、丁酸、戊酸、己酸）的方法。以Shim-pack SCR-102H色谱柱为分离柱,选用p-甲苯磺酸水溶液为流动相,考察了流动相中p-甲苯磺酸的浓度、流速、pH、色谱柱温度对分离和测定脂肪族有机酸的影响,确定了最佳的色谱条件为：0.2mmol/Lp-甲苯磺酸水溶液作为流动相,流速1.2mL/min,柱温45℃。所测有机酸的检测限为0.03-0.99mg/L,相对标准偏差在2.3%以下（n=5）,回收率为91.2%-105.6%,整个分析过程在28min内完成。该法用于白酒样品的分析,结果令人满意。

Some Ferrocene Derivatives of Acylhydrazones

The title organometallic compounds were synthesized by the condensation of formyl and acetyl ferrocene with cyanoacetyl, propionyl, butyryl, o furoyl, o thiofuroyl and m pyridinecarboxy hydrazine in anhydrous ethanol under reflux. The IR, 1H NMR, MS, and Mssbauer spectra for these compounds were recorded and are discussed.

The production of biobased diamines from renewable carbon sources: Current advances and perspectives

Bio-based diamines are considered to be a promising alternative to traditional fossil-fuel-based diamines,the important platform chemical for the synthesis of polymer materials.In this review,the current status of the art of the synthesis of aliphatic and aromatic diamines from renewable biomass are considered.In the case of aliphatic diamines,we describe strategies for biologically producing diamines with different carbon numbers including 1,3-diaminopropane,1,4-butanediamine,1,5-pentanediamine,1,6-diaminohexane,1,8-diaminooctane,1,10-diaminodecane,and 1,12-diaminododecane.In addition,aromatic diamines produced from various kinds of renewable biomass,including lignin,cashew nut shell,and terpenoids,are reviewed here.Furthermore,the application of typical diamines in synthesis of polyurethane and polyamide are also reviewed.

A density functional theory study on the decomposition of aliphatic hydrocarbons and cycloalkanes during coal pyrolysis in hydrogen plasma

To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from coal, were investigated. Methane and cyclohexane were chosen as the model compounds. Density functional theory was employed, and many reaction pathways were involved. Calculations were carried out in Gaussian 09 at the B3LYP/6-31G（d,p） level of the theory. The results indicate that the main pyrolysis products of methane and cyclohexane in hydrogen plasma are both hydrogen and acetylene, and the participation of active hydrogen atoms makes dehydrogenation reactions more favorable. H2 mainly comes from dehydrogenation process, while many reaction pathways are responsible for acetylene formation. During coal pyrolysis in hydrogen plasma, three main components in volatiles like aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons lead to the formation of hydrogen and acetylene, but their contributions to products distribution are different.

Impacts of plant secondary metabolites from conifer litter on the decomposition of Populus purdomii litter

A decomposition experiment of Populus purdomii litter,a commonly used afforestation species in the Qinling Mountains,China,was conducted.Water extracts of five conifer litters were used to treat P.purdomii litter and its soil.The P.purdomii litter was incubated at room temperature(20–25℃)and constant soil moisture for 6 months.During the decomposition period,the dynamics of litter mass and nutrient contents were detected to investigate the impacts of plant secondary metabolites.The results indicate that litter extracts of Pinus tabuliformis,Platycladus orientalis,Pinus armandii and Larix principisrupprechtii significantly inhibited the overall nutrient release of P.purdomii litter,while the last three types of litter extracts simultaneously inhibited its decomposition.Conversely,the litter extracts of Picea asperata significantly accelerated the overall nutrient release of P.purdomii.Generally,most of the conifer species,whose litter released terpenoids,phenolics,steroids,and aliphatic acids,will inhibit the decomposition and/or nutrient release from P.purdomii litter.Their negative effects on the decomposers and soil enzymatic activities indicates that planting diversity should be lower when mixed planted with P.purdomii.

Synthesis and properties of novel aliphatic polycarbonate from carbon dioxide with 1,2-butylene oxide and ε-caprolactone

A new degradable aliphatic poly(butylene-co-e-caprolactone carbonate) (PBCL) was synthesized through the terpolymerization of carbon dioxide, 1,2-butylene oxide (BO) and e-caprolactone (CL), a polymer supported bimetallic complex (PBM) was used as a catalyst. The terpolymers prepared were characterized by FT-IR,1H NMR, 13C NMR, WXRD and DSC. The hydrolysis tests were carried out to appraise the degradability of the copolymers.

Lithium bromide catalyzed solvent free method for synthesis of 2-substituted benzimidazoles and imidazopyridines

The first successful lithium bromide mediated solvent free condensation of arylenediamine and esters to obtain 2-substituted benzimidazole and imidazopyridine in good to excellent yields is described.

Molecular Design of Synthetic Biodegradable Polymersas Cell Scaffold Materials

Poly(lactic acid) and its copolymers are regarded as the most useful biomaterials. The good biocompatibility, biodegradability and mechanical properties of them make the synthetic biodegradable polymers have primary application to tissue engineering. The advantages and disadvantages of the synthetic biodegradable polymers as cell scaffold materials are evaluated. This article reviews the modification of polylactide-family aliphatic polymers to improve the cell affinity when the polymers are used as cell scaffolds. We have developed four main approaches: to modify polyester cell scaffolds in combination of plasma treating and collagen coating; to introduce hydrophilic segments into aliphatic polyester backbones; to introduce pendant functional groups into polyester chains; to modify polyester with dextran. The results of the cell cultures prove that the approaches mentioned above have improved the cell affinity of the polyesters and have modulated cell function such as adhesion, proliferation and migration.

Organic Carboxylate Ligand Tuned Topological Variations in Three Zn(Ⅱ)Coordination Polymers:Syntheses,Crystal Structures and Photoluminescent Properties

Three new Zn（Ⅱ） coordination polymers, namely [Zn2（suc）2（bib）2]n·nH2 O（1）, [Zn（glu）（bib）]n·4 nH2 O（2）, and [Zn（adp）（bib）]n（3）（bib = 1,4-bis（N-imidazolyl）butane, H2 suc = succinic acid, H2 glu = glutaric acid, H2 adp = adipic acid） have been hydrothermally synthesized and structurally characterized. Compound 1 features a 3D framework with 4-connected hxg-d topological network, compound 2 is comprised of 2D 44-sql-type sheets, and the adjacent 2D sheets are further packed into a 3D supramolecular architecture via intermolecular hydrogenbonding interactions, and compound 3 is a 3D framework with 4-fold interpenetrating dia topology. The structural comparison of these three compounds demonstrates that the topological variations can be well controlled by employing aliphatic dicarboxylate ligands with different spacer lengths. Moreover, the thermal stabilities and photoluminescent properties of them were also studied in detail.

Synthesis of aliphatic amidediol and used as a novel mixed plasticizer for thermoplastic starch

In this paper,aliphatic amidediol was synthesized and mixed with glycerol used as a plasticizer for preparing thermoplastic starch（AGPTPS）.The yield of aliphatic amidediol was 91%.FF-IR expressed that the mixture of aliphatic amidediol and glycerol formed stronger and stable hydrogen bond with starch molecules compared to the native cornstarch.By scanning electron microscope（SEM）native cornstarch granules were proved to transfer to a homogeneous continuous system.After being stored for a period time at room temperature,the mechanical properties of AGPTPS were also studied.As a mixed plasticizer,aliphatic amidediol and glycerol would be practical to extend TPS application scopes.

Synthesis of CO2 Copolymer Based Polyurethane Foams

CO2-copolymer based polyurethane foams were synthesized and characterized in this paper. The foams were found to have higher strength and lower heat of combustion than the conventional polyether polyurethane foams. They may find wide applications in many fields.

STRUCTURAL PHASE TRANSITION OF ALIPHATIC NYLONS VIEWED FROM THE WAXD/SAXS AND VIBRATIONAL SPECTRAL MEASUREMENTS AND MOLECULAR DYNAMICS CALCULATION

The crystalline phase transition of aliphatic nylon 10/10 has been investigated on the basis of the simultaneous measurement of wide-angle and small-angle X-ray scatterings, the infrared spectral measurement and the molecular dynamics calculation. An interpretation of infrared spectra taken for a series of nylon samples and the corresponding model compounds was successfully made, allowing us to assign the infrared bands of the planar-zigzag methylene segments reasonably. As a result the methylene segmental parts of molecular chains were found to experience an order-to-disorder transition in the Brill transition region, where the intermolecular hydrogen bonds are kept alive although the bond strength becomes weaker at higher temperature. The small-angle X-ray scattering data revealed a slight change in lamellar stacking mode in the transition region. The crystal structure has been found to change more remarkably in the temperature region immediately below the melting point, where the conformationally disordered chains experienced drastic rotational and translational motions without any constraints by hydrogen bonds, and the lamellar thickness increased largely along the chain axis. These experimental results were reasonably reproduced by the molecular dynamics calculation performed at the various temperatures.

Effect of the Structure of Cations and Anions of Ionic Liquids on Separation of Aromatics from Hydrocarbon Mixtures

The effects of the structure of typical cations and anions of ionic liquids on the separation of benzene and toluene from aromatic/paraffin mixtures were studied. The .results showed that the corresponding separation factors were considerably larger than those of the traditional solvents （Benzene＋Hexane＋sulfolane）, and that the ionic liquids could be used as novel solvents for the separation of aromatics from hydrocarbon mixtures. The key parameters governing the ability of ionic liquids for separating aromatics from hydrocarbon sources were investigated. It was found that the effectiveness of the ionic liquids, based on the same anion, changed in the cation order of [BIqu]^＋〈 [BPy]^＋〈 [BMIM]^＋. The selectivity of the ionic liquid toward aromatics decreased apparently with the increasing length of the substituted alkyl chain of its cationic head ring. The separation factors, based on the same cation, changed in the anion order of [Tf2N]^-〈[PF6]^-〈[BF4]^-〈[C2H5SO4]^-. The solubilities of the aromatics were greater in the ionic liquids based on the former three anions than that in the ionic liquids involving [C2H5SO4]^-.

Identification of MAM1s in Regulation of 3C Glucosinolates Accumulation in Allopolyploid Brassica juncea

Allopolyploid Brassica juncea is particularly enriched in sinigrin,a kind of 3C aliphatic glucosinolates(GSLs),giving rise to characteristic taste after picking.However,the molecular mechanism underlying 3C aliphatic GSLs biosynthesis in this species remains unknown.In this study,we genome-widely identified GSLs metabolic genes,indicating different evolutionary rate of GSLs metabolic genes between subgenomes of B.juncea.Eight methythioalkylmalate synthase(MAMs)homologs were identified from B.juncea,in which six MAM1s were located in chloroplast and the other two were not detected with any expression.Furthermore,BjMAM1-4,BjMAM1-5,and BjMAM1-6 displayed higher expression levels in leaves than other tissues.Silenced expression analysis revealed that BjMAM1-4 and BjMAM1-6 function in 3C and 4C aliphatic GSLs accumulation.The specificity of the substrate selection for the second cycle reaction is much lower than that of the first cycle,suggesting these genes may preferentially catalyze 3C aliphatic GSLs biosynthesis.Our study provides insights into the molecular mechanism underlying the accumulation of 3C aliphatic GSLs,thereby facilitating the manipulation of aliphatic GSLs content in B.juncea.

STUDIES ON MISCIBILITY OF POLY (ε-CAPROLACTONE) AND ALIPHATIC POLYCARBONATE BLENDS AND DETERMINATION OF THEIR INTERACTION PARAMETER

In this paper the miscibility of poly (ε-caprolactone) (PCL) and aliphatic polycarbonate (APC) is studied by using DSC. The results show that PCL and APC are miscible in all ranges of composition. The interaction parameter between the polymers is calculated from the melting point depression data. Using optical microscope, the shapes of the PCL spherulites in the blends are observed.

Investigating the crucial roles of aliphatic tails in disulfide bond-linked docetaxel prodrug nanoassemblies

Disulfide bond-bridging strategy has been extensively utilized to construct tumor specificity-responsive aliphatic prodrug nanoparticles(PNPs) for precise cancer therapy. Yet, there is no research shedding light on the impacts of the saturation and cis-trans configuration of aliphatic tails on the self-assembly capacity of disulfide bond-linked prodrugs and the in vivo delivery fate of PNPs. Herein, five disulfide bond-linked docetaxelfatty acid prodrugs are designed and synthesized by using stearic acid, elaidic acid, oleic acid, linoleic acid and linolenic acid as the aliphatic tails, respectively. Interestingly, the cistrans configuration of aliphatic tails significantly influences the self-assembly features of prodrugs, and elaidic acid-linked prodrug with a trans double bond show poor self-assembly capacity. Although the aliphatic tails have almost no effect on the redox-sensitive drug release and cytotoxicity, different aliphatic tails significantly influence the chemical stability of prodrugs and the colloidal stability of PNPs, thus affecting the in vivo pharmacokinetics, biodistribution and antitumor efficacy of PNPs. Our findings illustrate how aliphatic tails affect the assembly characteristic of disulfide bond-linked aliphatic prodrugs and the in vivo delivery fate of PNPs, and thus provide theoretical basis for future development of disulfide bond-bridged aliphatic prodrugs.