生物质在超临界水中热解行为的初步研究

在间歇式高压反应釜中，考察了生物质（稻杆）在超临界水中的热解行为，研究了热解产物分布随反应温度、压力以及停留时间的变化规律。结果表明,气体收率随温度升高而增加，油收率则先增加后减少，380 ℃～410 ℃产油量较大，可达28.57%；气体收率和油收率随压力升高而增加，残渣收率则明显减小，但当压力高于31.5 MPa后，油收率基本不再随压力的升高而变化；气体收率随停留时间的延长而增加，油收率则先增加后减少。     

非晶态聚对苯二甲酸乙二酯膜应力屈服机制的示差扫描量热研究

采用示差扫描量热法、应力应变测量研究了物理老化对非晶态聚对苯二甲酸乙二酯（ＰＥＴ）膜单轴拉伸过程中应力屈服行为的影响．结果表明，非晶高聚物经物理老化后屈服应力，应力屈服峰及热焓吸热峰均增大；屈服前后的ＤＳＣ结果表明，经过屈服点后试样热焓吸热峰消失，屈服后的试样经物理老化后，应力屈服峰又再现．从凝聚缠结的观点解释了非晶高聚物物理老化和应力屈服的本质．     

Yield stress analysis of 1D calcium and titanium precipitate-based giant electrorheological fluids

1D calcium and titanium composite nanorods synthesized were applied as electrorheological (ER) active materials with extremely high static yield stresses, i.e., giant ER effect. The yield stress of this giant ER fluid was analyzed using a new universal yield stress scaling equation in the form of the modified Bessel functions with two different limiting behaviors in a low and high electric field region. The universal yield stress equation collapsed the yield stress data onto a single curve.     

Methane coupling in microwave plasma under atmospheric pressure

Methane coupling in microwave plasma under atmospheric pressure has been investigated.The effects of molar ratio n(CH4)/n(H2),flow rate and microwave power on the reaction have been studied.(1)With the decrease of n(CH4)/n(H2)ratio,methane conversion,C2 hydrocarbon yield,energy yield and space-time yield of acetylene increased,but the yield of carbon deposit decreased.(2)With the increase of microwave power,energy yield of acetylene decreased,but space-time yield of acetylene increased.(3)With the increase of flow rate,energy yield and space-time yield of acetylene increased first and then decreased.Finally,under the reaction conditions of CH4 flow rate of 700 mL/min,n(CH4)/n(H2)ratio of 1/4 and microwave power of 400 W,the energy yield and space-time yield of acetylene could reach 0.337 mmol/kJ and 12.3 mol/(s m3),respectively.The reaction mechanism of methane coupling in microwave plasma has been investigated based on the thermodynamics of chemical reaction.Interestingly,the acetylene yield of methane coupling in microwave plasma was much higher than the maximum thermodynamic yield of acetylene.This phenomenon was tentatively explained from non-expansion work in the microwave plasma system.     

Some applications of the AMPC model of the shear yield stress of particulate fluids

The AMPC structural model of shear yield stress of single component suspensions is extended to three important rheological phenomena encountered in particulate fluids. These are shear yield stress of multi-component systems, time dependent shear yield stress of thixotropic suspensions, and compressive yield stress of particulate fluids. The shear yield stress of multi-component suspensions is modeled by summing the interparticle interactions due to all possible combinations of particle sizes and solid constituents. The time dependent shear yield stress of thixotropic muds is simulated by invoking the proportionality between yield stress and interparticle bond density across the shear plane. The compressive yield stress of particulate fluids is calculated by assuming that consolidation occurs by shear but at a narrower gap between the particles. The ability of the model to describe these diverse phenomena reasonably well seemingly validates its basic premise, namely, a 3-dimensional space-filling network of particles whose mechanical properties can be estimated from the theory of strength of particulate assemblage.     

Yield Stress Measurement of Dense Pastes with Pipe Transport and Vane

Yield stress is a key rheological parameter of dense paste. Considering practical utility and to estimate the possible slipping flow, yield stress measurements were carried out using the curve extrapolation method and vane method with rheometer in both controlled shear stress (CSS) and controlled shear rate (CSR) model. All measured yield stresses show to increase exponentially with concentration in different scale. The vane method yield stresses are both higher than the extrapolation curve yield stress. For the coal slurry used in this paper, the extrapolation curve yield stress is lower by 17–30% than the dynamic yield stress that obtained under test model CSR. It indicates that wall slip exists in pipeline transportation; meanwhile wall slip can reduce transportation resistance of dense paste to some extent.     

Chemiluminescence quantum yield in permanganate reduction reactions in acid medium

Chemiluminescence quantum yields for the reactions of permanganate with oxalic, tartaric, and citric acids; hydrazine; KBr; and FeSO₄ in aqueous solutions of sulfuric acid have been measured. The maximum quantum yield reaches 1.2 × 10^?5 einstein/mol with the chemiexcitation yield being 2%. Hence, the relatively low chemiluminescence quantum yield is due to a low yield of light emission by chemiexcited particles, rather than the low chemiexcitation yield.     

Double yielding in PA6/TPV‐MAH blends: Effect of crosslinking degree of the dispersed phase

Thermoplastic vulcanizates (TPVs) based on PP and EPDM (the ratio is 5:5) with different crosslinking degrees were prepared using different contents of phenolic resins, and then blended with polyamide 6 (PA6). The results indicated that with an increase in crosslinking degree, the double yielding phenomenon in PA6/TPV blends became more distinct, the yield stress of the first yield point and the yield stress difference of the two yield points decreased; however, the yield strain of the first yield point did not change with the increasing crosslinking degree of the TPV, but the yield strain of the second yield point increased, resulting in a more broadened yield region. The SEM results showed that with an increase in the crosslinking degree of TPV, the diameter of TPV increased in the core layer, and the orientation degree of TPV in the skin and subskin layer deceased, accompanying with a decrease of the ratio of length to diameter (L/D) of the droplets. The morphology evolution of the PA6/TPV blend during the tensile test was also studied, and the results agreed well with the model we proposed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 912–922, 2009     

WAVELENGTH DEPENDENCE OF THE QUANTUM YIELD FOR THE STRUCTURAL ISOMERIZATION OF BILIRUBIN

The quantum yield and the relative photochemical yield for lumirubin formation from bilirubin bound to human albumin were determined at eight wavelengths from 410 to 520 nm. The quantum yield averaged 0.0015 for irradiation between 450 and 490 nm. At 410 and 430 nm the quantum yield was slightly lower. At the long wavelength end of the absorption band, from 500 to 520 nm, the quantum yield averaged 0.003. The relative photochemical yield, normalized to constant fluence, was greatest at 500 nm.     

Synthesis of 1,2,4-trioxepanes and 1,2,4-trioxocanes via photooxygenation of homoallylic alcohols

Homoallylic alcohols 4a-d, easily accessible in two steps from cyclopropyl methyl ketone, underwent a highly regioselective reaction with singlet oxygen to yield gamma-hydroxyhydroperoxides 5a-d in 57-72% yield. Acid-catalyzed reaction of 5a-d with acetone, cyclopentanone, and cyclohexanone furnished 1,2,4-trioxepanes 8a-d, 9a-d, and 10a-d in good yields. Homoallylic alcohol 12 also underwent a highly regioselective photooxygenation to yield gamma-hydroxyhydroperoxide 13 in 67% yield, which on reaction with acetone, cyclopentanone, and cyclohexanone, furnished 1,2,4-trioxocanes 16-18 in 41-55% yield.     

Preparation and novel reduction reactions of vinamidinium salts.

Substituted acetic acids and formamides react in the presence of phosphorus oxychloride to yield the vinamidinium hexafluorophosphate salts 5a-d, 6a-d, and 7 in moderate to good unoptimized recrystallized yields (40-67%) as easily handled nonhygroscopic solids. The 1,3-differentially substituted vinamidinium salts 8 was prepared by amine exchange in 81% yield as are the cyclic diazapinium salts 9 and 10 in > 76% yield. The symmetrical 2-chlorovinamidinium 11 was prepared by displacement of 3 in 71% yield. The 2-chlorovinamidinium salts are cleanly reduced to the parent vinamidinium salts 12-16 using HI or PPh3/pTSA in up to 99% assay yield.     

Hetero Diels-Alder reactions of acyl phosphonates: synthesis of glycosyl type phosphonates

We have prepared glycosyl type phosphonates via hetero Diels-Alder (HDA) reactions of acyl phosphonates with electron rich dienes. HDA reactions of acyl phosphonates with Danishefsky’s diene required thermal activation to yield the desired dihydropyranones in good yield (70-91%). The reactions with Brassard’s diene involved Lewis acid promotion to yield the corresponding lactones, though in moderate yield (33-69%).     

固相多肽合成中王树脂和Fmoc/tBu酪氨酸成酯反应的研究

以Fmoc/tBu酪氨酸和王树脂为原料,分别探讨了对称酸酐法、活化酯法和2,6-二氯苯甲酰氯(DCB)法中各种因素对氨基酸与树脂成酯反应的影响。实验表明:对称酸酐法连接率低,而其它两种方法,通过筛选合适的反应介质,均能取得良好结果。在活化酯法中,使用强极性溶剂DMA,弱极性溶剂THF/DCM和混合溶剂45%DMF/THF,反应5h,连接率均可提高到90%以上;在DCB法中,使用弱极性溶剂THF时,反应3h,连接率可达99%。总之,DCB方法是酪氨酸和王树脂成酯反应的最好方法。     

Studies on enaminonitriles: A new synthesis of 1,3‐substituted pyrazole‐4‐carbonitrile

3‐Diethylaminoacrylonitrile ( 1 ) reacts with hydrazonyl halides ( 2a‐d ) to yield 1,3‐disubstituted pyrazole‐4‐carbonitriles 5a‐d. The acetyl 1‐p‐chlorophenylpyrazole‐4‐carbonitrile ( 5a ) condensed with hydrazine hydrate to yield the bishydrazone 10 and with dimethylformamide dimethylacetal to yield 1‐aryl‐3‐(3‐dimethylamino)acryloyl pyrazole‐4‐carbonitrile ( 11 ). This enamine reacts with hydrazine hydrate to yield the pyrazolylpyrazole ( 12 ) and with naphthoquinone to yield the 3‐naphthofuranoyl pyrazole 13. The pyra‐zolyl pyridine derivative 14 was obtained upon treatment of 11 with acetylacetone in the presence of ammonium acetate. Compound 11 was coupled with p‐chlorobenzene diazonium chloride to yield the hydrazone 16 that was coupled further with p‐chlorobenzenediazonium chloride to yield the formazane 18.     

Nitroimidazoles. IX. Synthesis of 2-acetyl-1-methyl-5-nitroimidazole

Manganese dioxide oxidation of 2-hydroxymethyl-1-methyl-5-nitroimidazole (6) gave 1-methyl-5-nitroimidazole-2-carboxaldehyde (7) in high yield. Reaction of diazomethane with 7 afforded the title compound 1 in low yield. Treatment of ethyl acid malonate with two equivalents of isopropylmagnesium bromide in THF and subsequent addition to 1-methyl-5-nitroimidazole-2-carbonylimidazolide (12) yielded ethyl (1-methyl-5-nitroimidazole-2-carbonyl)acetate (10) in 70% yield. Hydrolysis and decarboxylation of compound 10 gave the desired compound 1 in 97% yield.     

Synthesis of (-)-quinocarcin by directed condensation of alpha-amino aldehydes

An enantioselective synthesis of the natural antiproliferative agent quinocarcin was achieved by the directed condensation of optically active alpha-amino aldehyde intermediates. Condensation of the N-protected alpha-amino aldehyde 1, prepared in eight steps (19% yield) from (R,R)-pseudoephedrine glycinamide, with the C-protected alpha-amino aldehyde derivative 2, prepared in seven steps (34% yield) from (R,R)-pseudoephedrine glycinamide, afforded the corresponding imine in quantitative yield. Without isolation, direct treatment of this imine intermediate with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and hydrogen cyanide led to cleavage of the fluorenylmethoxycarbonyl (Fmoc) protective group followed by addition of cyanide (Strecker reaction) to form the bis-amino nitriles 3 as a mixture of diastereomers, in 91% yield. Treatment of the diastereomers 3 with trimethylsilyl cyanide and zinc chloride in 2,2,2-trifluoroethanol at 60 degrees C led to stepwise cyclization to form the tetracyclic product 4 (42% yield from 1 and 2). The latter intermediate was transformed into (-)-quinocarcin (1) in five steps (45% yield). The yield of quinocarcin was 19% from 1 and 2 (7 steps), and 4% from pseudoephedrine glycinamide (15 steps).     

Yield optimization in the kinetically controlled enzymic peptide synthesis

The yield and its time-dependence in acylenzyme mechanism-based enzymic peptide synthesis are controlled by the proteinase kinetic specificity. The maximum yield is limited by a non-equilibrium constant K_max. Both K_max and the time, t_max, taken to attain the maximum yield, are directly related to the enzyme kinetic parameters. These relationships allow kinetic determination of yield optimization in kinetically controlled enzymic peptide synthesis.     

Experimental verification of yield strength of polymeric line contact structures

Polymeric line contact structures are increasingly being used in engineering applications, so that the determination of the yield strength of the structures is of great importance. However, experimental investigation has shown that the current prediction of the yield strength in engineering provides conservative results relative to the actual yield behaviour of the structures. In the present study, a more accurate assessment for the yield strength of a line contact structure is proposed and, more importantly, this assessment was verified by a series of specially designed line contact tests based on optical full-field measurements. Specifically, the validity of this proposed assessment was examined by loading and unloading a polymeric line contact structure at different loading levels, and its accuracy was validated by singly loading line contact structures made from different polymeric materials until the occurrence of significant global plastic deformation. The experimental results confirmed that this proposed yield strength assessment enables accurate determination of the yield behaviour of line contact structures.     

Microwave-assisted rapid synthesis of methyl 2,4,5-trimethoxyphenylpropionate, a metabolite of Cordia alliodora

Microwave assisted condensation of asaronaldehyde (2) with malonic acid in piperidine-AcOH provides 2,4,5-trimethoxycinnamic acid (3) in 87% yield within 4 min, which upon further reduction with PdCl2- HCOOH-aq. NaOH gives 3-(2,4,5-trimethoxy)phenyl propionic acid (4) in 88% yield within 3 min. Esterification of 4 with MeOH-H+ gives methyl 2,4,5-trimethoxyphenylpropionate (1), a metabolite of Cordia alliodora, in 94% yield within 3 min (overall 69% yield).     

L'électrosynthèse,une alternative pour la synthèse de polycarbosilanes

The electrochemical reduction of chloromethyldimethylchlorosilane affords polycarbosilanes in high yields and this route constitutes a competitive route to 1,1,3,3-tetramethyl-1,3-disilacyclobutane formed in 34% crude yield. The solvent mixture was varied to yield its precursor, Cl(CH₂SiMe₂)₂Cl, in 43% yield after distillation, while electrosynthesis in the presence of dimethyldichlorosilane provided bis(dimethyl-chlorosilyl)methane, another polycarbosilane precursor, in 60% yield after distillation.