Role of methoxy and C_(α)-based substituents in electrochemical oxidation mechanisms and bond cleavage selectivity of β-O-4 lignin model compounds

In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanol have been selected and their electrochemical properties have been studied experimentally by cyclic voltammetry, and FT-IR spectroelectrochemistry. Combining with electrolysis products distribution analysis and density functional theory calculations, oxidation mechanisms of all six model dimers have been explored. In particular, a total effect from substituents of both para-methoxy(on the aryl ring closing to Cα) and Cα-OH on the oxidation mechanisms has been clearly observed, showing a significant selectivity on the Cα-Cβbond cleavage induced by electrochemical oxidations.

Decomposition of a β-O-4 lignin model compound over solid Cs-substituted polyoxometalates in anhydrous ethanol: acidity or redox property dependence?

Production o f aromatics from lignin has attracted much attention. Because of the coexistence of C-O and C-C bonds and their complex combinations in the lignin macromolecular network, a plausible roadmap for developing a lignin catalytic decomposition process could be developed by exploring the transformation mechanisms of various model compounds. Herein, decomposition of a lignin model compound, 2-phenoxyacetophenone （2-PAP）, was investigated over several ce-sium-exchanged polyoxometalate （Cs-POM） catalysts. Decomposition of 2-PAP can follow two dif-ferent mechanisms： an active hydrogen transfer mechanism or an oxonium cation mechanism. The mechanism for most reactions depends on the competition between the acidity and redox proper-ties of the catalysts. The catalysts of POMs perform the following functions： promoting active hy-drogen liberated from ethanol and causing formation of and then temporarily stabilizing oxonium cations from 2-PAP. The use of Cs-PMo, which with strong redox ability, enhances hydrogen libera-tion and promotes liberated hydrogen transfer to the reaction intermediates. As a consequence, complete conversion of 2-PAP （〉99%） with excellent selectivities to the desired products （98.6% for phenol and 91.1% for acetophenone） can be achieved.

Model Compounds of the Mn Cluster in Oxygen-evolving Complex of PSⅡ

Six model compounds have been synthesized and used for probing the structural features of the Mn cluster in oxygen_evolving complex (OEC) of photosystem Ⅱ (PSⅡ). The model compounds contain Mn 2(μ_O) 2 and μ_O_μ_carboxylato di_manganese structural units, which offer Mn—Mn, Mn……Mn, and Mn—O(N) structural parameters consistent with the corresponding data of the OEC in PSⅡ, implying that the Mn cluster in OEC may possess similar structural features. Two model compounds containing halide anion have been used for discussing the binding of Cl - to Mn in PSⅡ. It is suggested that in the five S states, ligand exchange would lead to the ligation of chloride to Mn in the S states with Mn of higher valence.

Hydrogen production via steam reforming of bio-oil model compounds over supported nickel catalysts

The steam reforming of four bio-oil model compounds（acetic acid,ethanol,acetone and phenol） was investigated over Ni-based catalysts supported on Al2O3 modified by Mg,Ce or Co in this paper.The activation process can improve the catalytic activity with the change of high-valence Ni（Ni2O3,NiO） to low-valence Ni（Ni,NiO）.Among these catalysts after activation,the Ce-Ni/Co catalyst showed the best catalytic activity for the steam reforming of all the four model compounds.After long-term experiment at 700°C and the S/C ratio of 9,the Ce-Ni/Co catalyst still maintained excellent stability for the steam reforming of the simulated bio-oil（mixed by the four compounds with the equal masses）.With CaO calcinated from calcium acetate as CO2 sorbent,the catalytic steam reforming experiment combined with continuous in situ CO2 adsorption was performed.With the comparison of the case without the adding of CO2 sorbent,the hydrogen concentration was dramatically improved from 74.8% to 92.3%,with the CO2 concentration obviously decreased from 19.90% to 1.88%.

Degradation of lignite model compounds by the action of white rot fungi

Three compounds modeled on the lignite structure were chosen for experimental degradation by different fungi strains. Culture conditions and extracellular enzyme activities were optimized. The growth curves of the strains were determined to study mycelium dry weight and protein content changes. Gas chromatography and infrared spectroscopy were used to detect changes of functional groups before and after the action of the fungi on the model compounds. Possible decomposition products and degrada-tion mechanisms were proposed. The research findings show that C. Versicolor and Golden Mushroom can grow in presence of the model compounds. The optimum culture conditions were a pH of 6.0, a carbon-nitrogen ratio of five and a Tween-80 concentration of 0.1%. Newly produced substances were found by gas chromatography. Infrared analysis showed that the model compounds degraded under the action of the microorganisms.

Immobilized laccase on magnetic nanoparticles for enhanced lignin model compounds degradation

As a natural aromatic polymer,lignin has great potential but limited industrial application due to its complex chemical structure.Among strategies for lignin conversion,biodegradation has attracted promising interest recently in term of efficiency,selectivity and mild condition.In order to overcome the issues of poor stability and non-reusability of enzyme in the biodegradation of lignin,this work explored a protocol of immobilized laccase on magnetic nanoparticles(MNPs)with rough surfaces for enhanced lignin model compounds degradation.Scanning electron microscope with energy dispersive spectrometer(SEM-EDS),flourier transformation infrared spectroscopy(FTIR)and thermal gravimetric analysis(TGA)were utilized to characterize the immobilization of laccase.The results showed a maximum activity recovery of 64.7%towards laccase when it was incubated with MNPs and glutaraldehyde(GA)with concentrations of 6 mg·ml^-1and 7.5 mg·ml^-1for 5 h,respectively.The immobilized laccase showed improved thermal stability and pH tolerance compared with free laccase,and remained more than 80%of its initial activity after 20 days of storage at 4℃.In addition,about 40%residual activity of the laccase remained after 8 times cycles.Gas chromatography–mass spectrometry(GC–MS)was utilized to characterize the products of lignin model compound degradation and activation,and the efficiency of immobilized laccase was calculated to be 1–5 times that of free laccase.It was proposed that the synergistic effect between MNPs and laccase displays an important role in the enhancement of stability and activity in lignin model compound biodegradation.

Study on reaction characteristics of phenolic hydroxyl in coal by using the model compound during direct coal liquefaction

The reaction characteristics of phenolic hydroxyl group were studied under the conditions of direct coal liquefaction. 2-naphthol was used as a coal model compound in this study. Under the conditions of with and without catalysts, a series of experiments were conducted at different temperatures, pressures and reaction time. Gas chromatography-mass spectrometry and gas chromatography were used to identify and quantify the reactants and products respectively. The conversion of 2-naphthol rises with the increase of reaction temperature, initial pressure and catalyst amount. The results indicated that tem- perature had a significant effect on 2-naphthol conversion, which promoted the dehydroxylation reaction. However, initial pressure had an important influence on the hydrogenation of 2-naphthol and naphthalene. The iron catalyst plays a significant role of cracking instead of hydrogenation. It is concluded that the harsh reaction conditions of high temperature, high pressure, and more catalyst are conducive to promoting dehydroxylation of 2-naphthol. The reaction mechanism was put forward based the experimental results, in which 2-tetralone was an intermediate.

Catalytic cracking mechanisms of tar model compounds

B3LYP/6-31G(d,p) method was used to investigate the catalytic cracking mechanism of biomass tar model compound.Phenol,toluene and benzene were selected as the tar model compounds and CaO was selected as the catalyst.The pathways of tar compound radical absorbed by CaO were determined firstly through comparing enthalpy changes of the absorption,and then Mulliken population changes were analyzed.The results show that the absorption of tar model compound radical and CaO is an exothermic reaction.Formation of C—O—Ca is more easily than that of C—Ca—O and formation of Caromatic—Caromatic—Ca—O is more easily than that of Caromatic—C(O)—Ca—O.The C—C bond Mulliken populations in tar model compound radicals are reduced by 11.9%,10.5% and 15.5% in the case of a hydrogen atom removed,and those are 15.7%,14.3% and 16.3% in the case of two hydrogen atoms removed through the absorption of CaO.Catalytic ability of CaO acting on the tar model compound is in an order of phenol>benzene>toluene.

Electrolytic reduction of Nantong coal and model compounds with oxygenic functional groups in an aqueous NaCl solution

Electrolytic reductions of oxygenic functional groups （OFGs） on coal surface and coal model compounds with OFGs in an aqueous NaCl solution are studied by electrochemical methods combined with GC/MS, GC and FFIR analyses. Different electrode reactions, their corresponding potentials and dynamic equations during the processes are investigated. The results show that benzoic acid, benzaldehyde, benzalcohol and hypnone are reduced to benzaldehyde and benzalcohol, methoxybenzene and benzal- cohol, toluene and styrene, respectively, at the cathode. The corresponding electrode potentials and dynamic equations are deter- mined. The.electrolytic reduction also leads to an increase in the contents of hydroxyl groups and aliphatic moieties and a corresponding decrease in those of carboxyl and carbonyl groups in Nantong coal, a high-sulfur coal, an enhancement in the flotation desulfurization of the coal. ER also reduces organic sulfur and FeS2 in the coal.

THE SYNTHESIS AND CRYSTAL STRUCTURE OF B-(32) MODEL COMPOUND: 1-C_4H_9Co(salen)(Py)

The title complex i-C_4H_9Co(salen)(Py) (Py=pyridine. salen=dianion of disalicylideneethylenediamine) has been first synthesized. Its crystal structure has been determined by X-ray diffraction method. The crystsis are monoclinic with space group P2_1/ C. The unit cell parametes are presented. The structure has been refined to a final R of 0.038.

Crosslinking Mechanism of Soy Protein-based Adhesives based on Glyoxal and a Compound of Protein Model

The crosslinking mechanism of glyoxal and asparagine was analyzed,and the relationship between the mechanism and practical performances of soy protein-based adhesives was also discussed.It is shown that when pH=1 and 3,glyoxal reacted with asparagine in the form of major cyclic ether compounds.When pH=5,glyoxal reacted with asparagine in two structural forms of sodium glycollate and cyclic ether compounds.However,amidogens of asparagine were easy to develop protonation under acid conditions.Supplemented by the instability of cyclic ether compounds,the reaction activity and reaction degree between glyoxal and asparagine were relatively small.Under alkaline conditions,glyoxal mainly reacted with asparagine in the form of sodium glycollate.With the increase of pH,the polycondensation was more sufficient and the produced polycondensation products were more stable.The reaction mechanism between glyoxal and asparagine had strong correspondence to the practical performances of the adhesives.Glyoxal solution could develop crosslinking reactions with soy protein under both acid and alkaline conditions.Bonding strength and water resistance of the prepared soy protein-based adhesives were increased significantly.When pH>7,glyoxal had relatively high reaction activity and reaction intensity with soy protein,and the prepared adhesives had high crosslinking density and cohesion strength,showing relatively high bonding strength,water resistance and thermal stability.

Persymmetric adaptive polarimetric detection of subspace range-spread targets in compound Gaussian sea clutter

This paper focuses on the adaptive detection of range and Doppler dual-spread targets in non-homogeneous and nonGaussian sea clutter.The sea clutter from two polarimetric channels is modeled as a compound-Gaussian model with different parameters,and the target is modeled as a subspace rangespread target model.The persymmetric structure is used to model the clutter covariance matrix,in order to reduce the reliance on secondary data of the designed detectors.Three adaptive polarimetric persymmetric detectors are designed based on the generalized likelihood ratio test(GLRT),Rao test,and Wald test.All the proposed detectors have constant falsealarm rate property with respect to the clutter texture,the speckle covariance matrix.Experimental results on simulated and measured data show that three adaptive detectors outperform the competitors in different clutter environments,and the proposed GLRT detector has the best detection performance under different parameters.

A study on some macrocyclic bicopper(Ⅱ) complexes as the model compounds of superoxide dismutase

24-Membered macrocyclic bicopper(Ⅱ) complexes wth bridging ligand imidzao-late,SCN-,N3-and H2O respectively were synthesized by condensation of diacetylpyridine with 3-oxapentane-1,5-diamine.As the model compounds of superoxide dismutase (SOD),the relationship between their SOD activities and properties of bridging ligands and redox potentials of copper(Ⅱ) were studied.

Competitive polycondensation of model compound melamine-urea-formaldehyed(MUF)resin system by^(13)C NMR

Melamine-urea-formaldehyde(MUF)resin is an excellent adhesive in the field of wood adhe-sives,however the competition mechanism is questionable which affects the structure control and performance optimization of the resin.In this study,the competitive resin synthesis poly-condensation reaction of MUF system under alkaline condition was studied based on the model compound 1,3-dihydroxymethyl urea(UF_(2))and melamine(M)system,and the competitive reac-tion mechanism in the system was deduced by^(13)C NMR quantitative analysis.The results show that the energy barrier of hydroxymethylation of melamine is lower than that of urea,and the priority of hydroxymethylation is lower;the addition of melamine results in a large amount of hy-drolysis of UF_(2),and the formed free formaldehyde,resulting in hydroxymethylation of melamine;there is obvious polycondensation reaction in UF_(2)+M system,mainly from the relationship be-tween hydroxymethylurea and melamine or hydroxymethylmelamine.The type I bridge bond structure of polycondensation mainly comes from the reaction of UF_(2) and M,which is difficult to form the type II bridge bond.At low molar ratio,the formation of bridge bond is superior to that of ether bond.With the increase of molar ratio,the formation of ether bond shows advantages,but there is obvious competition between them.There may be competitive presence of the UF self-condensation products,melamine-formaldehyde(MF)self-condensation products and MUF co-condensed products after the polycondensation reaction.

Synthesis of a trimeric lignin model compound composed of a-O-4 and b-O-4 linkages under microwave irradiation

A trimeric lignin model compound composed of α-O-4 and β-O-4 linkages was prepared by the microwave-assisted synthesis, which consisted of three steps： （a） the synthesis of 3-methoxy-4- benzyloxyacetophenone （2） from acetovanillone （1）, （b） the bromination of compound 2 to produce 3- methoxy-4-benzyloxy-α-bromoacetophenone （3）, and （c） followed by a nucleophilic substitution of compound （3） to obtain 3-methoxy-4-benzyloxy-α-（3-methoxy-4-（1-propenyl）phenol）-acetophenone （4）. The target product was characterized by MS, 1H NMR and 13C NMR spectroscopy. It was found that the trimeric compound synthesized can be used as a preferable lignin model compound because it contains guaiacyl structural unit （3-methoxy-4-hydroxy phenyl propane） linked by α-O-4 and β-O-4 linkages. In addition, under the conditions of microwave irradiation, the reaction time of each step is significantly reduced, and the selectivity of target product is greatly improved. The yields of each step and the overall sequence are 95.31%. 87.3%. 90.6% and 75.4% （95.31%× 87.3% × 90.6%）. respectively.

Steam reforming of toluene as a tar model compound with modified nickel-based catalyst

Catalytic steam reforming is a promising route for tar conversion to high energy syngas in the process of biomass gasification. However, the catalyst deactivation caused by the deposition of residual carbon is still a major challenge. In this paper, a modified Ni-based Ni-Co/Al2O3-CaO (Ni-Co/AC) catalyst and a conventional Ni/Al2O3 (Ni/A) catalyst were prepared and tested for tar catalytic removal in which toluene was selected as the model component. Experiments were conducted to reveal the influences of the reaction temperature and the ratio between steam to carbon on the toluene conversion and the hydrogen yield. The physicochemical properties of the modified Ni-based catalyst were determined by a series of characterization methods. The results indicated that the Ni-Co alloy was determined over the Ni-Co/AC catalyst. The doping of CaO and the presence of Ni-Co alloy promoted the performance of toluene catalytic dissociation over Ni-Co/AC catalyst compared with that over Ni/A catalyst. After testing in steam for 40 h, the carbon conversion over Ni-Co/AC maintained above 86% and its resistance to carbon deposition was superior to Ni/A catalyst.

Uniform asymptotics for finite-time ruin probability in some dependent compound risk models with constant interest rate

Consider two dependent renewal risk models with constant interest rate. By using some methods in the risk theory, uniform asymptotics for finite-time ruin probability is derived in a non-compound risk model, where claim sizes are upper tail asymptotically independent random variables with dominatedly varying tails, claim inter-arrival times follow the widely lower orthant dependent structure, and the total amount of premiums is a nonnegative stochastic process. Based on the obtained result, using the method of analysis for the tail probability of random sums, a similar result in a more complex and reasonable compound risk model is also obtained, where individual claim sizes are specialized to be extended negatively dependent and accident inter-arrival times are still widely lower orthant dependent, and both the claim sizes and the claim number have dominatedly varying tails.

Inhibition of Model Compound of Purple Acid Phosphatases on Growth of Aerobacter aerogenes Investigated by Microcalorimetry

Microcalorimetry was used to study the inhibitory or antibiotic action of six kinds of the model compounds of purple acid phosphatases on a strain of Aerobacter aerogenes . Difference in their capacities to inhibit the metabolism of this bacterium was observed. The extent and duration of the inhibitory effect on the metabolism as judged from the growth rate constant, k , and the half inhibitory concentration, IC 50 , varied with the different drugs. The rate constant k of A. aerogenes (in the log phase) in the presence of the compounds decreased with the increasing of concentrations. The experimental results reveal that the order of the antibiotic activity of the compounds is: LD 1>LD 2>LD 3>XF 1>LD 4～LD 5.

EXPECTED PRESENT VALUE OF TOTAL DIVIDENDS IN THE COMPOUND BINOMIAL MODEL WITH DELAYED CLAIMS AND RANDOM INCOME

In this paper, a compound binomial model with a constant dividend barrier and random income is considered. Two types of individual claims, main claims and by-claims, are defined, where every by-claim is induced by the main claim and may be delayed for one time period with a certain probability. The premium income is assumed to another binomial process to capture the uncertainty of the customer＇s arrivals and payments. A system of difference equations with certain boundary conditions for the expected present value of total dividend payments prior to ruin is derived and solved. Explicit results are obtained when the claim sizes are Kn distributed or the claim size distributions have finite support. Numerical results are also provided to illustrate the impact of the delay of by-claims on the expected present value of dividends.