Poly Ethylene Glycols as Efficient Media for the Synthesis of <i>β</i>-Nitro Styrenes from <i>α</i>, <i>β</i>-Unsaturated Carboxylic Acids and Metal Nitrates under Conventional and Non-Conventional Conditions

Poly ethylene glycols (PEG-200, 400, 600, 4000 and 6000) supported reactions were conducted with certain α, β-unsaturated acids in presence of metal nitrates under solvent free (solid state) and mineral acid free conditions. The reactants were ground in a mortar with a pestle for about 30 minutes. The aromatic acids underwent nitro decarboxylation and afforded β-nitro styrene derivatives in very good yield while α, β-unsaturated aliphatic carboxylic acids gave corresponding nitro derivatives. Addition of PEG accelerated rate of the reaction enormously. Reaction times substantially decreased from several hours to few minutes followed by highly significant increase in the product yield. Among the several PEGs PEG-300 has been found to be much more effective than other PEGs.

Poly Ethylene Glycols (PEG) and Micelles as Efficient Catalysts for the Oxidation of Xanthine Derivatives under Conventional and Non-Conventional Conditions

Oxidation of Xanthine alkaloid have been studied with various one and two electron oxidizing agents using PEGs and micelle forming surfactants. The reaction is too sluggish in solution phase, but moderately fast in presence of PEGs and micelles. However, the reactions are dramatically enhanced under microwave irradiations. Present protocol has several advantages, such as solvent-free conditions, during work-up, fast reaction times, high yields, eco-friendly operational and experimental simplicity, readily available additives as catalysts.

Reversed ethane/ethylene adsorption in a metal–organic framework via introduction of oxygen

Separation of ethane from ethylene is a very important but challenging process in the petrochemical industry.Finding an alternative method would reduce the energy needed to make 170 million tons of ethylene manufactured worldwide each year.Adsorptive separation using C2H6-selective porous materials to directly produce high-purity C2H4 is more energy-efficient.We herein report the"reversed C2H6/C2H4 adsorption"in a metal–organic framework Cr-BTC via the introduction of oxygen on its open metal sites.The oxidized Cr-BTC(O2)can bind C2H6 over C2H4 through the active Cr-superoxo sites,which was elucidated by the gas sorption isotherms and density functional theory calculations.This material thus exhibits a good performance for the separation of 50/50 C2H6/C2H4 mixtures to produce 99.99%pure C2H4 in a single separation operation.

Electromechanical Properties of Ethylene Propylene Diene Elastomers: Effect of Ethylene Norbornene Content

Ethylene propylene diene elastomers (EPDM) of various side chains and molecular weights were prepared as thin discs and the effects of electric field strength and temperature on the electromechanical properties were investigated. The electrical conductivity, the dielectric constant, the storage and loss moduli (G' and G'), the storage modulus response (ΔG’1000 V/mm), and the storage modulus sensitivity (ΔG’1000 V/mm/G’0) of the elastomers of different ethylene norbornene (ENB) contents and molecular weights were measured under electric field strengths varying from 0 V/mm to 1000 V/mm and at temperatures between 300 K and 380 K. The storage modulus response and sensitivity increase with increasing molecular weight and dielectric constant, consistent with the existing theory. However, for the case of EPDMs with different ENB contents, the storage modulus response and sensitivity vary inversely with the dielectric constant. EDPM is potentially a new type of electroactive materials.

Analysis of residual crosslinking agent content in UV cross-linked poly(ethylene oxide) hydrogels for dermatological application by gas chromatography

Acrylates have been widely used in the synthesis of pharmaceutical polymers. The quantitation of residual acrylate monomers is vital as they are strong irritants and allergens, but after polymerization, are relatively inert, causing no irritation and allergies. Poly(ethylene oxide)(PEO) hydrogels were prepared using pentaerythritol tetra-acrylate(PETRA) as UV crosslinking agent. A simple, accurate, and robust quantitation method was developed based on gas chromatographic techniques(GC), which is suitable for routine analysis of residual PETRA monomers in these hydrogels. Unreacted PETRA was initially identified using gas chromatography–mass spectrometry(GC–MS). The quantitation of analyte was performed and validated using gas chromatography equipped with a flame ionization detector(GC–FID). A linear relationship was obtained over the range of 0.0002%–0.0450%(m/m) with a correlation coefficient(r2)greater than 0.99. The recovery( 4 90%), intra-day precision(%RSD o 0.67), inter-day precision(%RSD o2.5%), and robustness(%RSD o1.62%) of the method were within the acceptable values. The limit of detection(LOD) and limit of quantitation(LOQ) were 0.0001%(m/m) and 0.0002%(m/m), respectively.This assay provides a simple and quick way of screening for residual acrylate monomer in hydrogels.

Crystallization Behavior of Copolymer Poly(ethylene terephth-alate/isophthalate)(IPET)

The non-isothermal crystallization kinetics, isothermal crystallization and the morphology of crystals of the copolymer poly (ethylene terephthalate/ isophthalate )(IPET) were studied by DSC and polarized-light microscopy in this paper. DSC results indicate that the glass transition temperature Tg of IPET is slightly lower than that of poly(ethylene terephthalate) (PET), but the melting temperature Tm and the crystallization temperature Tc of PET and IPET have much difference.The difference of Tc between PET and IPET2 is about 7℃, and the difference of Tm between PET and IPET2 is about 16℃. From the kinetics analysis of the crystallization, the crystallization mechanism of all samples is of three-dimension spherulitic growth from instantaneous nuclei and the incorporation of isophthalate (IPA) decreases the crystallization rate of IPET greatly. The isothermal results indicate that the morphologies of PET and IPET crystals are all spherulite, which is in conformity to the results of nonisothermal dynamic crystallization. At the same time,the spherulite of IPET grows slower and has longer incubation time than the spherulite of PET under the same crystallization condition.

Simple Preparation of Halogen-Substituted <i>α</i>-Diimine Nickel Complexes Immobilized into Clay Interlayer as Catalysts for Ethylene Oligo-/Polymerization

In the practical use for the production of the α-olefins, it is highly desired to develop a novel heterogeneous catalyst system. The metal complexes immobilized into the clay interlayers show a great potential as heterogeneous catalysts due to their excellent processability. In this study, nine types of heterogeneous procatalyst Ln/Ni2+-micas were synthesized via a one-pot preparation method, which includes both the condensation reaction of the ligand derivatives and the intercalation of the ligands into the Ni2+ ion-exchanged fluorotetrasilicic mica interlayer. The ligand structures of the prepared procatalysts were [Ln: R-N = C(Nap)-C(Nap) = N-R] [(Nap = 1,8-naphthdiyl) (L1, R = 2-MePh;L2, R = 2-FPh;L3, R = 2-BrPh;L4, R = 4-MePh;L5, R = 4-FPh;L6, R = 4-BrPh;L7, R = 2,4-F2Ph;L8, R = 2,4-Br2Ph;L9, R = 2,6-F2Ph). At 50℃ and 0.7 MPaethylene pressure, the triisobutylaluminum-activated L1-L6/Ni2+-mica showed a catalytic activity for the ethylene oligo-/polymerization in the range of 334 - 549 g-ethylene&bull;g-cat–1&bull;h–1. A high catalyst activity was obtained when the substituent having a larger steric bulk than that of a methyl substituent was introduced at the ortho-position of the aryl rings. The introduction of the fluorine substituent as a strong electron-withdrawing group to the para-position also increased the catalytic activity. The L2, L4, L5, and L6/Ni2+-micas showed moderate selectivities to oligomers consisting of C4-C20 in the range of 19.9 - 41.6 wt% at 50℃. The calculated Schulz-Flory constants α based on the mole fraction of C12 and C14 were within 0.61 - 0.78.

Mechanical, Thermal and Crystallization Properties of Polypropylene (PP) Reinforced Composites with High Density Polyethylene (HDPE) as Matrix

Our work aims to evaluate a complete outlook of virgin high density polyethylene (HDPE) and polypropylene (PP) polyblends. Virgin PP of 20, 30 and 50 weight% is compounded with virgin HDPE. The properties like tensile strength, flexural strength, Izod impact strength are examined. Scanning electron microscopy (SEM) and polarised light microscopy (PLM) are used to observe the surface and crystal morphology. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) tests verify the non compatibility of both polymers. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) techniques are used to study the thermal behaviour of composites. The results manifest co-occurring spherulites for polyblends;indicating the composite to be a physical blend of continuous and dispersed phases, but on the other hand PP improves the tensile and flexural properties of HDPE.

Effect of ethylene vinyl acetate content on the performance of VMD using HDPE co-blending membrane

Membranes were fabricated with high-density polyethylene (HDPE) and ethylene vinyl acetate (EVA) blend through thermally induced phase separation and were then used for vacuum membrane distillation (VMD). The membranes were supported by non woven polyester fabric with a special cellular structure. Different membrane samples were obtained by adjusting the polymer concentration, HDPE/EVA weight ratio, and coagulation bath temperature. The membranes were characterized by scanning electron microscopy (SEM) analysis, contact angle test, and evaluation of porosity and pore size distribution. A series of VMD tests were conducted using aqueous NaCI solution (0.5 mol·L^-1) at a feed temperature of 65 ℃ and permeate side absolute pressure of 3 kPa. The membranes showed excellent performance in water permeation flux, salt rejection, and long-term sta-bility. The HDPE/EVA co-blending membranes exhibited the largest permeation flux of 23.87 kg·m^-2·h^-1, and benign salt rejection of ≥99.9%.

Energy Efficiency Evaluation Based on Data Envelopment Analysis Integrated Analytic Hierarchy Process in Ethylene Production

Energy efficiency data from ethylene production equipment are of high dimension, dynamic and time sequential, so their evaluation is affected by many factors. Abnormal data from ethylene production are eliminated through consistency test, making the data consumption uniform to improve the comparability of data. Due to the limit of input and output data of decision making unit in data envelopment analysis(DEA), the energy efficiency data from the same technology in a certain year are disposed monthly using DEA. The DEA data of energy efficiency from the same technology are weighted and fused using analytic hierarchy process. The energy efficiency data from different technologies are evaluated by their relative effectiveness to find the direction of energy saving and consumption reduction.

Ethylene response factor BnERF2-like (ERF2.4) from Brassica napus L.enhances submergence tolerance and alleviates oxidative damage caused by submergence in Arabidopsis thaliana

Ethylene response factor proteins play an important role in regulating a variety of stress responses in plants,but their exact functions in submergence stress are not well understood.In this study,we isolated BnE RF2.4 from Brassica napus L.to study its function in submergence tolerance.The expression of the BnE RF2.4 gene in B.napus and the expression of antioxidant enzyme genes in transgenic Arabidopsis were analyzed by quantitative RT-PCR.The expression of BnE RF2.4 was induced by submergence in B.napus and the overexpression of BnE RF2.4 in Arabidopsis increased the level of tolerance to submergence and oxidative stress.A histochemical method detected lower levels of H_2O_2,O^(·-)_2and malondialdehyde(MDA) in transgenic Arabidopsis.Compared to the wild type,transgenic lines also had higher soluble sugar content and higher activity of antioxidant enzymes,which helped to protect plants against the oxidative damage caused by submergence.It was concluded that BnE RF2.4 increased the tolerance of plants to submergence stress and may be involved in regulating soluble sugar content and the antioxidant system in defense against submergence stress.

Improvement of low temperature activity and stability of Ni catalysts with addition of Pt for hydrogen production via steam reforming of ethylene glycol

Hydrogen production by steam reforming of ethylene glycol(EG) at 300℃ was investigated over SiO2 and CeO2 supported Pt–Ni bimetallic catalysts prepared by incipient wetness impregnation methods. It was observed that impregnation sequence of Pt and Ni can affect the performance of catalysts apparently. Catalyst with Pt first and then Ni addition showed higher EG conversion and H2 yield owing to the Ni enrichment on the surface and the proper interaction between Pt and Ni. It was observed that although SiO2 supported catalysts exhibited better activity and H2 selectivity, CeO2 supported ones had better stability. This is attributed to the less coke formation on CeO2. Increasing Pt/Ni ratio enhanced the reaction activity, and Pt3–Ni7 catalysts with 3 wt% Pt and 7 wt% Ni showed the highest activity and stability. Ni surficial enrichment facilitated the C-C bond rupture and water gas shift reactions;and Pt addition inhibited methanation reaction. Electron transfer and hydrogen spillover from Pt to Ni suppressed carbon deposition. These combined effects lead to the excellent performance of Pt3–Ni7 supported catalysts.

Ethylene accelerates maize leaf senescence in response to nitrogen deficiency by regulating chlorophyll metabolism and autophagy

Leaf senescence is an orderly and highly coordinated process,and finely regulated by ethylene and nitrogen(N),ultimately affecting grain yield and nitrogen-use efficiency(NUE).However,the underlying regulatory mechanisms on the crosstalk between ethylene-and N-regulated leaf senescence remain a mystery in maize.In this study,ethylene biosynthesis gene ZmACS7 overexpressing(OE-ZmACS7)plants were used to study the role of ethylene regulating leaf senescence in response to N deficiency,and they exhibited the premature leaf senescence accompanied by increased ethylene release,decreased chlorophyll content and F_v/F_m ratio,and accelerated chloroplast degradation.Then,we investigated the dynamics changes of transcriptome reprogramming underlying ethylene-accelerated leaf senescence in response to N deficiency.The differentially expressed genes(DEGs)involved in chlorophyll biosynthesis were significantly down-regulated,while DEGs involved in chlorophyll degradation and autophagy processes were significantly up-regulated,especially in OE-ZmACS7 plants in response to N deficiency.A gene regulatory network(GRN)was predicted during ethylene-accelerated leaf senescence in response to N deficiency.Three transcription factors(TFs)ZmHSF4,Zmb HLH106,and ZmEREB147 were identified as the key regulatory genes,which targeted chlorophyll biosynthesis gene ZmLES22,chlorophyll degradation gene ZmNYC1,and autophagy-related gene ZmATG5,respectively.Furthermore,ethylene signaling key genes might be located upstream of these TFs,generating the signaling cascade networks during ethylene-accelerated leaf senescence in response to N deficiency.Collectively,these findings improve our molecular knowledge of ethylene-accelerated maize leaf senescence in response to N deficiency,which is promising to improve NUE by manipulating the progress of leaf senescence in maize.

A validated, related substance, GC method for 1,4-cyclohexanedione mono-ethylene Ketal

ABSTRACT A simple, economic, and time-efficient related substance, GC method has been developed for the analysis of 1,4-Cyclohexanedione mono- ethylene ketal(will be specified as ketal) in the presence of a potential impurity 1,4-cyclohexa- nedione bis (ethylene ketal) [will be specified as diketal]. Successful chromatographic separa- tion of the ketal from the impurity was achieved on a DBWAX ETR, 30 m x 0.32 mm x 1.0μ FT column with nitrogen as carrier gas and FID detector. The method was validated for linearity, accuracy, precision, and specificity and can be used for quality control during manufacture of ketal. A validated GC method is reported for the ketal for the first time.

Reaction pathways and selectivity in the chemo-catalytic conversion of cellulose and its derivatives to ethylene glycol:A review

Biomass-to-ethylene glycol is an effective means to achieve high-value utilisation of cellulose but is hindered by low conversion efficiency and poor catalyst activity and stability.Glucose and cellobiose are derivatives of cellulose conversion to ethylene glycol,and it is found that studying the reaction process of both can help to understand the reaction mechanism of cellulose.It is desirable to develop a reusable,highly active catalyst to convert cellulose into ethylene glycol.This ideal catalyst might have one or more active sites described the conversion steps above.Here,we discuss the catalyst development of celluloseto-ethylene glycol,including tungsten,tin,lanthanide,and other transition metal catalysts,and special attention is given to the reaction mechanism and kinetics for preparing ethylene glycol from cellulose,and the economic advantages of biomass-to-ethylene glycol are briefly introduced.The insights given in this review will facilitate further development of efficient catalysts,for addressing the global energy crisis and climate change related to the use of fossil fuels.

Sn nucleation and growth from Sn(II)dissolved in ethylene glycol:Electrochemical behavior and temperature effect

Thermodynamic and kinetic aspects of Sn nucleation and growth processes onto a glassy carbon electrode from SnCl2·2H2O dissolved in ethylene glycol solutions were studied.Typical reduction and oxidation peaks observed in voltammograms have demonstrated the capability of ethylene glycol solutions to electrodeposit Sn.The temperature-dependence of diffusion coefficient values derived from potentiodynamic and potentiostatic studies helped to determine and validate estimations of the activation energy for Sn(II)bulk diffusion.Chronoamperometric results have identified that,the suitable model to describe the early stage of Sn electrodeposition could be composed of Sn three-dimensional nucleation and diffusion-controlled growth and water reduction contributions,which was duly validated by theoretical and experimental approaches.From the model,typical kinetic parameters such as the nucleation frequency of Sn(A),number density of Sn nuclei(N_(0)),and diffusion coefficient of Sn(II)ions(D),were determined.The presence of Sn nuclei with excellent quality and their structures were verified using SEM,EDX,and XRD techniques.

Effect of introducing oxygen into ethylene tar pitches on their carbonaceous products

Ethylene tar is a prospective precursor for preparing carbonaceous materials,which is regarded as a representative soft carbon material after carbonization.However,the introduction of oxygen can influence the morphology of the final carbonaceous materials.For the introduction of oxygen,dealkylation and dehydrogenation will be promoted and the molecules can be linked more effectively.For the subsequent carbonization,the biphenyl structures caused by the deoxygenation via the elimination of CO_(2),as well as the reserved aromatic ether bonds,can facilitate the strong cross-linking,which will restrain the movement of the carbon layers and the formation of the graphitic structures.After the graphitization treatment at 2800℃,the oxidized pitch can lead to short-range ordered and long-range unordered structures,while the sample without oxidation can result in long-range ordered graphitic structures.It can be proved that a simple oxidation-carbonization treatment can transform ethylene tar into hard carbon structures.

Boosting kinetic separation of ethylene and ethane on microporous materials via crystal size control

The adsorptive separation of C_(2)H_(4)and C_(2)H_(6),as an alternative to distillation units consuming high energy,is a promising yet challenging research.The great similarity in the molecular size of C_(2)H_(4)and C_(2)H_(6)brings challenges to the regulation of adsorbents to realize efficient dynamic separation.Herein,we reported the enhancement of the kinetic separation of C_(2)H_(4)/C_(2)H_(6)by controlling the crystal size of ZnAtzPO_(4)(Atz=3-amino-1,2,4-triazole)to amplify the diffusion difference of C_(2)H_(4)and C_(2)H_(6).Through adjusting the synthesis temperature,reactant concentration,and ligands/metal ions molar ratio,ZnAtzPO4 crystals with different sizes were obtained.Both single-component kinetic adsorption tests and binary-component dynamic breakthrough experiments confirmed the enhancement of the dynamic separation of C_(2)H_(4)/C_(2)H_(6)with the increase in the crystal size of ZnAtzPO_(4).The separation selectivity of C_(2)H_(4)/C_(2)H_(6)increased from 1.3 to 98.5 with the increase in the crystal size of ZnAtzPO_(4).This work demonstrated the role of morphology and size control of adsorbent crystals in the improvement of the C_(2)H_(4)/C_(2)H_(6)kinetic separation performance.

Unraveling the incompatibility mechanism of ethylene carbonate-based electrolytes in sodium metal anodes

Ethylene carbonate(EC)is widely used in lithium-ion batteries due to its optimal overall performance with satisfactory conductivity,relatively stable solid electrolyte interphase(SEI),and wide electrochemical window.EC is also the most widely used electrolyte solvent in sodium ion batteries.However,compared to lithium metal,sodium metal(Na)shows higher activity and reacts violently with EC-based electrolyte(NaPF_(6)as solute),which leads to the failure of sodium metal batteries(SMBs).Herein,we reveal the electrochemical instability mechanism of EC on sodium metal battery,and find that the com-bination of EC and NaPF_(6) is electrically reduced in sodium metal anode during charging,resulting in the reduction of the first coulombic efficiency,and the continuous consumption of electrolyte leads to the cell failure.To address the above issues,an additive modified linear carbonate-based electrolyte is provided as a substitute for EC based electrolytes.Specifically,ethyl methyl carbonate(EMC)and dimethyl carbon-ate(DMC)as solvents and fluoroethylene carbonate(FEC)as SEI-forming additive have been identified as the optimal solvent for NaFP_(6)based electrolyte and used in Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7))/Na batteries.The batter-ies exhibit excellent capacity retention rate of about 80%over 1000 cycles at a cut-off voltage of 4.3 V.