Efficient catalytic conversion of carbohydrates into 5-ethoxymethylfurfural over MIL-101-based sulfated porous coordination polymers

In this work, a series of MIL-101-SO3H(x) polymeric materials were prepared and further used for the first time as efficient heterogeneous catalysts for the conversion of fructose-based carbohydrates into 5-ethoxymethylfurfural(EMF) in a renewable mixed solvent system consisting of ethanol and tetrahydrofuran(THF). The influence of –SO3H content on the acidity as well as on the catalytic activity of the porous coordination polymers in EMF production was also studied. High EMF yields of 67.7% and 54.2% could be successively obtained from fructose and inulin in the presence of MIL-101-SO_3H(100) at 130 °C for 15 h.The catalyst could be reused for five times without significant loss of its activity and the recovery process was facile and simple. This work provides a new platform by application of porous coordination polymers(PCPs) for the production of the potential liquid fuel molecule EMF from biomass in a sustainable solvent system.     

Dehydration of glucose into 5-hydroxymethylfurfural in SO_3H-functionalized ionic liquids

The continuous dehydration of D-glucose into 5-hydroxymethylfurfural（HMF） was carried out under mild conditions,using SO3H-functionalized acidic ionic liquids as catalysts and H2O-4-methyl-2-pentanone（MIBK） biphasic system as solvent.High glucose conversion of 97.4% with HMF yield of 75.1%was obtained at 120 8C for 360 min,also,small amounts of levulinic acid（LA） and formic acid were generated.Generally,the dosage of catalyst and the initial content of glucose influenced the reaction significantly; the HMF selectivity decreased with the excessive elevation of temperature and prolonging of time; and water content in the system had a negative effect on the reaction.The ionic liquid catalyst could be recycled and exhibited constant activity for five successful runs.This paper provided a new strategy for HMF production from glucose.     

Uniaxial alignment of poly(3-hexylthiophene) nanofibers by zone-casting approach

The preparation of large area coverage of films with uniaxially aligned poly(3-hexylthiophene)(P3HT) nanofibers by using zone-casting approach is reported.The length and the orientation of the nanofibers are defined by the solubility of the solvent,the P3HT molecular weight and the substrate temperature.The length of the oriented nanofibers could be increased from 1 μm to more than 10 μm by adding poor solvent into the P3HT solution.It is found that for P3HT of relatively low molecular weight,a solvent with relatively low solubility has to be chosen to get the oriented film.While for the high molecular weight P3HT,the solvent with a relatively high solubility has to be used.The well-aligned film could be obtained because of the solute concentration gradient in the region where the critical concentration is reached during the zone-casting process.Particularly,the solvent evaporation rate and crystallization rate must be chosen properly to satisfy the stationary conditions above,which were controlled by an appropriate choice of solvent and substrate temperature.The film prepared by zone-casting approach had microcrystalline P3HT domains with more inter-chain order than spin-coating film.Meanwhile,the P3HT π-π stacking direction was parallel to the alignment direction of the nanofibers.     

Controlled acid hydrolysis and kinetics of flavone C-glycosides from trollflowers

Acid hydrolysis mechanisms of orientin-2"-O-galactopyranoside(OGA),orientin and other flavone C-glycosides in the trollflowers[Trollius chinensis Bunge) were studied in this report for the first time.Hydrolysis parameters including temperature,acidity,solvent and reaction time were comprehensively investigated.OGA could be hydrolyzed to orientin,followed by an isomerization to isoorientin via a reversible Wessely-Moser rearrangement reaction under stronger acidic conditions.A first-order kinetic model fitted the hydrolysis process of OGA well.Under the optimal hydrolysis conditions of 80 ℃,1.0 mol/L H~+ and 7 h reaction time,about 77%OGA was transformed to orientin with no detectable isoorientin.These results could be helpful for better understanding of the acid hydrolysis kinetics of flavone C-glycosides,as well as the preparation of these valuable components under controlled acid hydrolysis conditions.     

Catalytic transformation of cellulose and its derived carbohydrates into chemicals involving C–C bond cleavage

The catalytic transformation of cellulose, the major component of abundant and renewable lignocellulosic biomass, into building-block chemicals is a key to establishing sustainable chemical processes. Cellulose is a polymer of glucose and a lot research effort has been devoted to the conversion of cellulose to six-carbon platform compounds such as glucose and glucose derivatives through C–O bond activation. There also exist considerable studies on the catalytic cleavage of C–C bonds in biomass for the production of high-value chemicals, in particular polyols and organic acids such as ethylene glycol and lactic acid. This review article highlights recent advances in the development of new catalytic systems and new strategies for the selective cleavage of C–C bonds in cellulose and its derived carbohydrates under inert, reductive and oxidative atmospheres to produce C1–C5polyols and organic acids. The key factors that influence the catalytic performance will be clarified to provide insights for the design of more efficient catalysts for the transformation of cellulose with precise cleavage of C–C bonds to high-value chemicals. The reaction mechanisms will also be discussed to understand deeply how the selective cleavage of C–C bonds can be achieved in biomass.     

Reverse-phase high-performance liquid chromatography of virus proteins and other hydrophobic proteins

Summary So far most solvents generally used in reverse phase chromatography (RPC) for separation of peptides and water soluble polypeptides could not be utilized for hydrophobic proteins such as membrane proteins and structural polypeptides of viruses due to their insufficient solubility. But we have introduced a new RP-HPLC solvent system which was very useful in our studies on poliovirus polypeptides. Formic acid in high concentration is an extremely potent solvent for proteins, particularly those that are hydrophobic. Preliminary estimates are made of the concentration of formic acid which is required to completely dissolve hydrophobic proteins. For example, solubilization of structural polypeptides of poliovirus which are absolutely water insoluble requires 60% formic acid. Therefore, we used a proportion of 60% formic acid in all solvents for reversed phase chromatography and applied propanol-2 or acetonitrile as the organic modifiers for gradient elution. Using this mobile phase all four poliovirus polypeptides of three serological types were obtained in high purity by this rapid procedure. In each case, polypeptides were quantitatively eluted independent of the amount of protein (1–1000 μg) injected onto the columns. The solvents used were volatile and easily removed in a short evaporation step. Therefore this solvent system is suited for analytical and for micropreparative separation of proteins for chemical, biochemical and immunological studies. Rechromatography and electrophoresis in SDS-polyacrylamide gels of the separated polypeptides demonstrated that this solvent system with its high proportion of formic acid did not alter their primary structure. There may have been major changes in secondary and tertiary structure. In contrast, alterations of the elution characteristics were observed after reduction of disulfide bridges and several modifications of proteins. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

GAS SORPTION,DIFFUSION AND PERMEATION OF ORDERED POLYMERIC MEMBRANES

He, CO_2, O_2, N_2, CH_4, C_3H_8, and t-C_4H_(10) gas permeability coefficients and diffusion coefficients of poly(4-methylpentene-1) (PMP) with various degrees of crystallization were plotted against the degree of crystallization. The plotdemonstrated a linear relationship. The gas permeability coefficient and diffusion coefficient of pure amorphous and purecrystalline PMPs were evaluated by a linear extrapolation to zero and 100% crystallinity, respectively. The relationshipbetween the diffusion coefficient of crystalline parts of PMP and the kinetic diameter of penetrant gases was discussed.Syndiotactic polystyrene (SPS) could exist as δ form crystals complexed with organic solvents such as benzene, toluene,xylene, and ethylbenzene. The mesophase of SPS is prepared by annealing the δ form of crystalline complexes at a certaintemperature for 1 h. The desorption of solvent during annealing almost does not result in changes of both the conformation ofbackbone chains and the crystal lattice. We could prepare the mesophase containing molecular cavities with the size andshape of the organic solvent molecules. The mesophase could sorb the same solvent after the manner of Langmuir sorption atlow vapor pressure range while this would not be the case for solvents of different size and shape. This suggests a molecularrecognition of organic solvent, and mesophase SPS might be useful for separation membrane and adsorptive material.     

Effects of Hydrogen-bonding Interaction and Polarity on Emission Spectrum of Naphthalene-Triethylamine in Mixed Solvent

The effects of the protic and aprotic polar solvents on the emission spectrum of the naphthalene-triethyl-amine system in THF were studied under conditions of steady-state illumination. The fluorescence spectrum of the naphthalene-triethylamine system consists of two emission bands, the fluorescence band of naphthalene (band A, 329 nm) and the emission band of the exciplex(band B, 468 nm). The intensities of both the emission bands decrease with increasing the solvent polarity. The intensity of band B also decreases due to the hy-drogen-bonding interaction between triethylamine and protic solvent, while that of band A increases. It is thus suggested that the quenching of naphthalene fluorescence by triethylamine in THF occurs through the charge transfer and electron transfer reactions. The spectral changes upon the increase of solvent polarity can be explained by the dependences of the equilibrium constant between exciplex and ion-pair and the rate constant for the electron transfer reaction from triethyl.amine to the excited naphthalene on the rel.ative permittivity of solvent. It is shown that the formation of intermolecular hydrogen-bonding between triethylamine and protic solvent suppresses the quenching reaction by the decrease in free amine. Acetonitrile has only a polar effect and trichloroacetic acid only a hydrogen-bonding(or protonation) effect, while alcohols have both the effects. The effects of alcohols could be separated into the effects of solvent polarity and intermolecular hy-drogen-bonding interaction quantitatively.     

Enantioselective epoxidation of nonfunctionalized alkenes catalyzed by recyclable new homochiral bis-diamine-bridged bi-Mn(salen) complexes

Three new homochiral bis-diamine-bridged bi-Mn(salen) complexes were synthesized. Their catalysis on asymmetric epoxidation of α-methylstyrene, styrene and indene was studied with NaClO and m-CPBA as oxidants respectively. This homogeneous catalyst exhibited comparable catalytic activity and enantioselectivity to the Jacobsen’s catalyst in the asymmetric epoxidation of unfunctionalized olefins. Furthermore, the catalyst could be conveniently recovered and reused at least five times without significant losses of both activity and enantioselectivity. Specially, it also could be efficiently used in large-scale reactions with superior catalytic disposition being maintained at the same level, which provided the potential for the applications in industry. The effect of axial bases, temperature and solvent on activity and enantioselectivity of the catalytic system were also studied.     

An Expedient Method for the Synthesis of Thiosemicarbazones under Microwave Irradiation in Solvent-free Medium

A simple,efficient and eco-friendly method for the synthesis of thiosemicarbazones from thiosemicarbazidesand aldehyde under microwave irradiation has been reported,and no solvent and catalyst were used.And the tech-nique of microwave irradiation coupled with solvent-free condition proved to be a quite valuable method in the or-ganic synthesis.     

Reactions in a Mixture of CH_4 and CO_2 under the Action of Microwave Discharge at Atmospheric Pressure

Reactions between CH_4 and CO_2 under the action of continuous microwave discharge at atmospheric pressure were studied in a special homemade reactor. The main products were CO and H2, while acetylene and ethylene were also found in the products. Experimental results show that conversions of CH4 and CO2 could be higher than 90% without the presence of any catalyst. Effects of CO2/CH4 molar ratio and total flow rate of the feed gas on the reaction were also investigated.     

Analysis of volatile compounds in Herba Asari by single-drop micro-extraction gas chromatography mass spectrometry

A rapid headspace single-drop micro-extraction(mix) gas chromatography mass spectrometry(SDMEGC -MS) for the analysis of the volatile compounds in Herba Asari was developed in this study.A mixed solvent of n-tridecane and butyl acetate(1:1) was finally used for the extraction at 70 C for 15 min with sample amount of 0.750 g and 100 mesh particle size.Under the determined conditions,the pound samples of Herba Asari were directly applied for the analysis.SDME-GC-MS,SPME-GC-MS and SD-GCMS methods were compared and the results showed that SDME-GC-MS method was a simple, inexpensive and effective way to measure the volatile compounds in Herba Asari and could be used for the analysis of volatile compounds in complex samples.     

Reactions in a Mixture of CH4 and CO2 under the Aciton of Microwave Discharge at Atmospheric Pressure

Reactions between CH4 and CO2 under the action of continuous microwave discharge at atmospheric pressure were studied in a special homemade reactor,The main products were CO and H2,while acetylene and ethylene were also found in the products.Experimental results show that conversions of CH4 and CO2 could be higher than 90% without the presence of any catalyst,Effects of CO2/CH4 molar ratio and total flow rate of the feed gas on the reaction were also investigated.     

Kinetic study of propane dehydrogenation and catalyst deactivation over Pt-Sn/Al2O3 catalyst

The kinetics of propane dehydrogenation and catalyst deactivation over Pt-Sn/Al2O3 catalyst were studied.Performance test runs were carried out in a fixed-bed integral reactor.Using a power-law rate expression for the surface reaction kinetics and independent law for deactivation kinetics,the experimental data were analyzed both by integral and a novel differential method of analysis and the results were compared.To avoid fluctuation of time-derivatives of conversion required for differential analysis,the conversion-time data were first fitted with appropriate functions.While the time-zero and rate constant of reaction were largely insensitive to the function employed,the rate constant of deactivation was much more sensitive to the function form.The advantage of the proposed differential method,however,is that the integration of the rate expression is not necessary which otherwise could be complicated or impossible.It was also found that the reaction is not limited by external and internal mass transfer limitations,implying that the employed kinetics could be considered as intrinsic ones.     

Extraction of Catechin Compounds from Green Tea with a New Green Solvent

An emerging green solvent called a deep eutectic solvent（DES） was applied to the extraction and determination of catechin（C）,（＋）epicatechin gailate（ECG） and （-）epigallocatechin gallate（EGCG） from Chinese green tea.After evaluating different combinations of them by extraction methods and DESs,a DES-based extraction method was established and optimized by a systematic investigation of the influencing factors.As a result,a total of 3.629,35.25 or 114.2 mg/g catechin,（＋）epicatechin gallate or （-）epigaliocatechin gallate were extracted respectively under optimal conditions with extraction efficiencies of 82.7％,92.3％ and 97.0％,respectively.By comparing with other common used solvents for extracting catechin compounds,DESs were proved to be potential extraction solvents for bioactive ingredients.     

Heck Reaction Catalyzed by Palladacycle in Neat Water

Cydopalladated ferrocenylimine has been found to be a type of excellent phosphine-free catalyst for Heck reactions in neat water with both higher yields and turnover numbers than those reported in the literature up to now. Some commercial emulsifying agents, indodin~ the commonly used quaternary ammonium salts, have been proved to be excellent additives in the catalysis of the reactions. Not only aromatic iodide, but also aromatic bromide could be coupled with the olef‘ms. All rcactions were able to be conducted in air under refluxlng condition.     

Enzymatic Promiscuity： Escherichia coli BioH Esterase-catalysed Aldol Reaction and Knoevenagel Reaction

Esterase BioH,which is obligatory for biotin synthesis in Escherichia coli,was found to exhibit a promiscuous ability to catalyse Aldol and Knoevenagel reactions with moderate to good yields.The reaction conditions including organic solvent,molar ratio of ketone to aldehyde,enzyme amount,and reaction time were investigated to evaluate the effect of different reaction conditions on yield.Target compounds were afforded in the best yield of 91.2％ for Aldol reaction and 54.7％ for Knoevenagel reaction.In addition,because the enzyme could be prepared with a low cost,this protocol could provide an economic route to conduct Aldol and Knoevenagel reactions,which expand the field of enzymatic promiscuity.     

固体酸Fe2(SO4)3催化合成丙酸异戊酯

Solid acid ferric sulphate Fe2(SO4)3 was prepared and used for the study of the catalytic synthesis of iso-amyl propionate. The optimun reaction conditions were follows: the ratio of amount of substance n(iso-amylalcohol) : n(propionic acid) = 1.5, the reaction time 2h, the catalyst quantity 1.5g, and dewatering solvent toluene 10ml. The yield was 97.2% under the optimum reaction conditions. The catalyst being of high catalytic activity for the esterification reactions was prepared very easily and could be used repeatedly.     

Evaporation-induced Morphology Pattern of Triblock Copolymer A5B10C5 in Thin Film： a Multibody DPD Simulation Study

We used multibody dissipative particle dynamics method,by which the attractive and repulsive interactions can be effectively considered,to investigate the evaporation-induced morphology patterns of triblock copolymer A5B10C5 in thin film.With changing attractive interactions between solvent vapor and triblock copolymer that represent various selective solvents,lamellar morphology,sandwich lamellar morphology,spherical morphology and disorder morphology patterns of the thin films were obtained for both coil-coil-coil and rod-coil-coil chain architectures,respectively.The order parameter and the film thickness were calculated during the process for characterizing the film properties,and it was found that the rigid A-block of the triblock copolymer hinders the formation of an ordered structure.     

Study on the alkylation reaction of guanine and N-acetylguanine and the synthesis of 1''''-C alkylated carba-DHPG analogues

The alkylation reaction of guanine and N-acetylguanine with model compounds such as isopropyl bromide or 4-heptyl tosylate were studied. The reaction conditions such as temperature, solvent, base, and catalyst were examined for their effects on the reaction rate, and the yield and regioselectivity of the coupling reaction. The highest yield was obtained by using DMSO as the solvent. The reaction proceeded in a homogenous manner to give higher yield of 9-N and 7-N substituted product in a mole ratio of 1:1. The ratio could be raised to 2:1 if dibenzo-18-crown-6 was used as a catalyst. Using the above procedure, three carba-DHPG analogues bearing different 1'-C alkyl side chains were synthesized.