SYNTHESIS AND CHARACTERIZATION OF POLY{4-[2-(tert-BUTYLDIMETHYLSILOXY)ETHYL]STYRENE}AND ITS HYDROLYSIS DERIVATIVE

The living cationic polymerization of 4-[2-(tert-butyldimethylsiloxy)ethyl]styrene (TBDMES) was studied in methylcyclohexane (MeChx)/methylchloride (MeCl) (50/50 V/V) solvent mixture at -80 degrees C. The initiator 1,1-diphenylethylene (DPE) capped 2-chloro-2,4,4-trimethylpentane (TMPCl) was formed in situ in conjunction with titanium tetrachloride (TiCl(4)). The Lewis acidity of TiCl(4) was decreased by the addition of titanium(IV) isopropoxide (Ti(OiPr)(4)) to accomplish living polymerization of TBDMES. Hydrolysis of poly(TBDMES) in the presence of tetra-butylammonium fluoride yielded poly[4-(2-hydroxyethyl)styrene] (poly(HOES)). FT-IR, NMR and DSC demonstrated the hydrolysis was complete.

Pig Liver Esterase-catalyzed Hydrolysis of Three Diesters of meso-Bicyclic Dicarboxylic Acid and Three Tetraesters of Tetrahydrofuran -2,3,4,5-tetracarboxylic Acid

Three diesters of exo- syn-meso-oxabicyclo (2, 2, 1 ) -hept- 5- ene- 2, 3- dicarboxylic acid and three tetraesters of tetrahydrofuran-2, 3, 4, 5-tetracarboxylic acid were synthesized and tested with enantioselective hydrolysis catalyzed by pig liver esterase(PLE). The results of the PLEcatalyzed hydrolysis were discussed.

Alkaline Hydrolysis of PP/EHDPET Blend Fibers

Polypropylene superfine fibers or cell porous fibers were prepared from the bi-component blend fibers of polypropylene/easlly hydro-degraded polyester(PP/EHDPET)by alkaline hydrolysis process. EHDPET is a kind of copolyester that can be rapidly hydro-degraded in the hot alkaline solution. This paper discussed the kinetics of alkaline hydrolysis of EHDPET, and the effect of catalyst, bulk ratio and the content of polypropylene grafted maleic anhydride (PP-g-MAH) on the alkaline hydrolysis process. Meanwhile, the morphological change of the outer surface of blend fibers during this process was also investigated by the technology of scanning electron microscope (SEM).

Quantum Chemical Calculation on Preparation of YBa＿2Cu＿3O＿（7－δ） Powders by Hydrolysis of Metal Alkoxides

The structural characteristics of different alkoxides of Y. Ba and Cu are studied with quantum chemi-cal CNDO /2 calculations. The relative hydrolysis rate coefficients k_M of them are obtained according tothe relationship between frontier orbitals and organic chemical reactions. Based on the above results. properexperimental conditions for the preparation of homogeneous ultra-purity. submicro high-T_cYBa_2Cu_3O_(7-δ) superconducting powders are proposed.

水解酸化-SBR-混凝工艺处理榨菜废水试验研究

通过水解酸化-SBR-混凝工艺处理榨菜废水试验得出,在水解酸化池HRT为6h,SBR条件为0.5h进水+10h好氧+4h厌氧+1h沉淀+0.5h闲置(曝气量6L·min-1,污泥浓度4000mg·L-1),混凝试验PAC和PAM投加量分别为300mg·L-1和6mg·L-1条件下,COD、SS、氨氮和总磷平均去除率分别为96%、85.03%、84.9%和95.32%,出水水质达到污水综合排放标准二级标准。

Enantio-selective preparation of (S)-1-phenylethanol by a novel marine GDSL lipase MT6 with reverse stereo-selectivity

We previously functionally characterized a novel marine microbial GDSL lipase MT6 and identified that the stereo-selectivity of MT6 was opposite to that of other common lipases in trans-esterification reactions.Herein,we have investigated the use of MT6 in stereo-selective biocatalysis through direct hydrolysis reactions.Notably,the stereo-selectivity of MT6 was also demonstrated to be opposite to that of other common lipases in hydrolysis reactions.Parameters,including temperature,organic co-solvents,pH,ionic strength,catalyst loading,substrate concentration,and reaction time,affecting the enzymatic resolution of racemic 1-phenylethyl acetate were further investigated,with the e.e.of the final（S）-l-Phenylethanol product and the conversion being 97%and 28.5%,respectively,after process optimization.The lengths of side chains of 1-phenylethyl esters greatly affected the stereo-selectivity and conversion during kinetic resolutions.MT6 is a novel marine microbial GDSL lipase exhibiting opposite stereo-selectivities than other common lipases in both trans-esterification reactions and hydrolysis reactions.

Chemistry and Application of Phosphonium and Arsonium Ylide(ⅩⅧ)——Stereoselective Syntheses of (Z)-3-Perfluoroalkyl--4-(3-Carboethoxy-2-f uranyl )-3-Butenoates

The stereoselective syntheses of (Z)-methyl 3-perfluoroalkyl-4-(3-carboethoxy-2-furanyl)-3-butenoates 5a-c were investigated. The reaction of (3-carboethoxy-2-fu-ranyl)-methyltriphenylphosphonium bromide 1 with methyl 2-perfluoroalkynoates 2a-c in the presence of K2CO3 at room temperature gives two adducts, (E)-methyl 3-per-fluoroalkyl-4-( 3-carboethoxy-2-furanyl )-2-triphenylphosphoranylidene-3-butenoates 3a-c and (E)-methyl 3-perfluoroalkyl-4-(3-carboethoxy-2-furanyl)-4-triphenylphos-phoranylidene-2-butenoates 4a-c. (Z)-Methyl 3-perfluoroalkyl-4-(3-carboethoxy-2-furanyl)-3-butenoates 5a-c can be synthesized stereoselectively with high yields when an aqueous DMF solution of 3c, 4c or a mixture of 3a-b and 4a-b was heated at 140℃ for 8 h.

Synthesis of 3-O-Benzoyl-1 ,2-O-isopropylidene-a-D-allofuranose and Its Dimesylated Derivative

Diisopropylidenated α-D-glucofuranose （1） was oxidated with CrO3-pyridine complex. Oxidated product and its hydrate were separated and were reduced together to synthesize diisopropylidenated α-D-allofuranose （ 3）. The yield of 3 increased by 8% than that with only oxidated product as reduction substrate. Benzoylated derivative of 3 was selectively nydrolyzed and dimesylated to synthesize 3-O-benzoyl-1 .2- O- isopropylidene-α-D-allofuranose （ 5 ） and its dimesylated derivative respectively. The overall yield of 5 from 1 was 36%. Each step and final products were analyzed by ^1H-NMR spectra and other methods. The experiments showed that the influence of acetic acid concentration on selective hydrolysis was obvious. The hydrolysis yield was 81.8%. Oxidation. reduction and other procedures were practical and had application potential.

Chlorinated Perylene Monoimide Monoanhydrate Synthesized via Hydrolysis and Its Application in Organic Solar Cells

Perylene-3,4-(dicarboxylic monoimide)-9,10-(dicarboxylic monoanhydrate)(PIA)is one key intermediate to construct functionalized perylene diimides(PDIs)for various applications.However,the difficulty in synthesizing chlorinated PIA hinders the study of chlorinated PDIbased materials.Although chlorination has been widely used to modify the properties of organic semiconductors.We successfully synthesize chlorinated PIA via a simple hydrolysis reaction using LiOH as the base,then a PDI dimer connected at the imide position,N-di-PDI-4Cl,is synthesized as an application example of chlorinated PIA.The heavily chlorinated PDI dimer exhibits deeper energy levels,slightly blue-shifted UV-Vis absorption compared to the non-chlorinated analogue.In addition,the photovoltaic performance of N-di-PDI-4Cl is characterized.This study paves one easy way to synthesize chlorinated PIA and its more delicate derivatives.

Theoretical study on the hydrolysis mechanism of N,N-dimethyl-N′-(2′,3′-dideoxy-3′-thiacytidine)formamidine

The hydrolysis mechanisms of N,N-dimethyl-N′-(2′,3′-dideoxy-3′-thiacytidine)formamidine (FA-3TC) in the gas phase and in aqueous solution were studied by use of the density functional theory B3LYP/6-31+G(d, p) method. Two possible reaction pathways in the title reaction were considered. In one pathway water attacks the C=N double bond first (path A) while in the other water attacks the C—N single bond first (path B). The calculated results indicate that the first step in both pathways is the rate-limiting process and path A is more favorable than path B in the gas phase. The effect of solvent water on the title reaction was assessed at the B3LYP/6-31+G(d, p) level of theory based on the po-larizable continuum model (CPCM). In water the first mechanism (path A) is also favored.

pH对厨余废物两相厌氧消化中水解和酸化过程的影响

通过间歇实验探讨了pH对厨余废物两相厌氧消化中水解和产酸过程的影响,详细考查了厨余废物在4个pH(pH =5 ,7,9,11)条件下的水解率、挥发酸(VFA)产量和速率、有机酸的组分和水解酸化产物的分配.实验结果表明,控制pH为7时,厨余废物具有更高的水解和酸化率,以水解酸化液体中TOC、COD与固液混合液中总COD、TOC比值表示的厨余废物水解率在实验第9d分别达到86%和82 % ,VFA浓度在实验第4d达到3 6g·L- 1 ,VFA产量是未调节pH时的2倍.在pH为7时,水解酸化产物中乳酸浓度相对较低,VFA中主要以丁酸和乙酸为主,丙酸很少.控制pH为7不但可以提高水解酸化效率,而且为后续产甲烷过程提供了更有利的基质。

温度对厨余垃圾两相厌氧消化中水解和酸化过程的影响

实验考查了厨余垃圾在4个温度(25℃、37℃、40℃、50℃)条件下的水解率、挥发酸(VFA)产量和速率、乳酸产量和有机酸的组成.结果表明:温度对水解和酸化过程均有较大影响,在小于37℃范围内水解率和酸化率均随温度升高而增加,最大的VFA浓度在37℃下获得,达34.4g/L.超过37℃,酸化率下降而水解率继续增加,最大水解率在50℃下获得达82%.VFA中以甲酸和乙酸为主,并有少量丙酸和丁酸产生,同时乳酸浓度一直较高.通过实验确定了厨余垃圾水解酸化过程的最优温度条件为37℃.

pH值对易腐有机垃圾厌氧发酵产物分布的影响

易腐有机垃圾的厌氧发酵（水解和酸化）程度和发酵类型受pH值的影响,批式实验结果表明：发酵液pH=7时有利于微生物的生长繁殖，从而促进碳水化合物的水解和酸化过程，还能促进可溶性蛋白的酸化过程，在不同pH值条件下，易腐有机垃圾的基本发酵类型为：pH=7时主要进行丁酸发酵；pH=8时丁酸发酵类型逐渐占优势；而pH=5时丙酸发酵类型逐渐占优势，乳酸是酸化初期的主要产物，但在发酵液的pH=5和pH=7条件下，乳酸可被微生物进一步代谢，而pH=8时乳酸却未能被代谢．在酸化初期醇的产生最大于挥发性脂肪酸，酸化后期pH=5和pH=7时挥发性脂肪酸与醇产生量比值为1．2～1．5：1，而pH=8时两者比值为1．6～2．5：1．pH为5、7和8二者的水解速率常数kh分别为0．0008h^-1、0．0009h^-1和0．0002h^-1．pH=7在反应时间r〉100h以后，发酵液中可溶态总有机碳全部山酸化产物组成，酸化完全；而pH=5和pH=8达到酸化完全的反应时间分别为t〉300h和t〉600h．

pH值对有机垃圾厌氧水解和酸化速率的影响

通过易腐性有机垃圾的批式厌氧发酵实验，比较不同的发酵液pH值对水解和酸化速率的影响．结果表明，发酵液的pH值为5—7时有利于颗粒态有机物的水解；在pH值不控制及pH值为5,6，7，8条件下，微生物处于静止生长期时，水解速率常数K分别为6．81×10^-5．57×10^-4,3．51×10^-4,7．55×10^-4,2．47×10^-4h^-1．发酵液pH=7时最有利于微生物的合成代谢，从而促进碳水化合物和蛋白质的水解过程和酸化过程，表现为代谢产物如乙醇、乙酸、丁酸和氨氮的大量生成，以及其他代谢产物种类的增加；pH=5和pH=6时，反应后期能促进酸化过程；pH=8时，会抑制酸化过程；对pH值不控制时，严重抑制水解和酸化过程．

pH调节方法对厨余垃圾两相厌氧消化中水解和酸化过程的影响

通过间歇实验探讨了pH调节方法对厨余垃圾两相厌氧消化中水解酸化过程和水解酸化液中Na+浓度的影响.实验比较了厨余垃圾在3种pH调节方法(利用NaOH溶液调节初始进料pH到7,利用NaOH和Ca(OH)2混合碱液每12h调节pH到7和利用调节C/N比调节pH到7)下水解酸化液中的Na+浓度、一级水解速率常数、挥发酸(VFA)浓度、乳酸浓度和VFA组分分配.结果表明,与利用NaOH溶液每12h调节pH相比较,3种pH调节方法都能够有效降低水解酸化出料液中的Na+浓度,但利用调节C/N比来调节pH能够取得更高的水解酸化效率,一级水解速率常数可以达到0.199d-1,VFA浓度在实验第3天即可达到35g·L-1.发酵产物乳酸在实验第2天即达到高峰浓度24g·L-1,后逐渐下降到6g·L-1,VFA组分中丙酸不是优势组分.

温度和料液浓度对牛粪高浓度厌氧水解酸化的影响

该文在室温为20℃的实验室条件下,对牛粪进行了批量式高浓度厌氧发酵试验,在以往研究的基础上进一步探讨发酵物料温度为32℃、35℃和40℃,料液浓度为9%和10%,发酵时间为12d时,温度和料液浓度对牛粪高浓度水解酸化的影响情况,找出较优的厌氧水解酸化条件。结果表明,当温度分别为32℃、35℃和40℃时,水解酸化产物各主要成份的含量差异较小,但在日均挥发性脂肪酸CODVFA产率方面32℃要远高于35℃和40℃,32℃和40℃之间的差值最大可达452mg/(L·d),约占最大日均CODVFA产率1227.00mg/(L·d)的37%;当料液浓度为9%和10%时,水解酸化产物各主要成份的含量差值较小,而在日均CODVFA产率方面9%组要远高于10%,差值最大可达463.38mg/(L·d),约占最大日均CODVFA产率1227.00mg/(L·d)的37.77%,因此牛粪高浓度厌氧水解酸化过程的较优工艺条件为温度32℃,料液浓度9%,发酵时间6d。

影响牛粪高浓度水解酸化过程中乙酸含量的因素研究

在室温为20℃的实验室条件下,对牛粪进行了批量式高浓度厌氧发酵,采用二次正交旋转组合设计试验方法,探讨牛粪水解酸化过程中,温度、料液浓度和停留时间对乙酸含量的影响规律。温度、料液浓度和停留时间的取值范围分别为25～35℃、6%～10%和2～12d,利用单因素分析法确定各因素在二次非线性模型中的主次顺序。利用频数分析找出各因素的最佳试验范围。结果表明,停留时间对乙酸含量的影响最大,温度次之,料液浓度的影响最小。通过频数分析,得出了在温度为26～30℃、料液浓度为7%～9%、停留时间为2～5d时挥发酸中的乙酸含量均高于66%。当温度为26～30℃、料液浓度为10%、停留时间为10～12d时挥发酸中的乙酸含量均低于60%。

温度波动对牛粪高浓度水解酸化特性的影响

以新鲜牛粪为原料,用自制的厌氧水解酸化系统研究了在高浓度两相厌氧发酵过程中,30℃和35℃时温度波动±2.5℃对挥发性脂肪酸产量和挥发性脂肪酸主要成分的影响。结果表明,温度波动对挥发性脂肪酸产量的影响因基础温度而异,在35℃时温度波动组的挥发性脂肪酸产量略高于恒温组,30℃时温度波动组的挥发性脂肪酸产量与恒温组基本持平,但总体趋势是温度波动组要好于恒温组。温度波动对乙酸含量基本没有影响,而对丙酸的含量有一定影响。所以在牛粪高浓度水解酸化过程中,可以在水解酸化相通过温度波动取得较好的厌氧水解酸化效果。

牛粪高浓度水解酸化过程丙酸含量的影响因素研究

在室温为20℃的实验室条件下,对牛粪进行了批量式高浓度厌氧发酵,采用二次正交旋转组合设计试验方法,探讨了牛粪水解酸化过程中,温度、料液浓度和停留时间对丙酸含量的影响规律。温度、料液浓度和停留时间的取值范围分别为25～35℃、6%～10%和2～12d,利用单因素分析法确定各因素在二次非线性模型中的主次顺序,利用频数分析找出各因素的最佳试验范围。试验分析结果表明,停留时间对丙酸含量的影响最大,温度次之,料液浓度的影响最小。通过频数分析,得出当温度为30～33℃,料液浓度为8%～10%,停留时间为10～12d时挥发酸中的丙酸含量均高于23%;当温度为25～31℃、料液浓度为7%～9%、停留时间为2～8d时挥发酸中的丙酸含量均低于19%。

厌氧折流板反应器处理垃圾渗滤混合废水

对厌氧折流板反应器（ＡＢＲ）处理城市污水与垃圾渗滤液混合废水过程中的水解酸化作用及污泥特性进行了研究。结果表明，ＡＢＲ可有效地改善混合废水的可生化性。进水ＢＯＤ５／ＣＯＤ为０．２～０．３时，出水ＢＯＤ５／ＣＯＤ可提高至０．４～０．６；容积负荷达４．７１ｋｇＣＯＤ／（ｍ３·ｄ）时，形成沉降性能良好、粒径为１～５ｍｍ的棒状颗粒污泥，各隔室中的污泥浓度为２０～３８ｇ／Ｌ。混合废水经ＡＢＲ的预处理，大大促进了废水进一步好氧处理的运行稳定性。