聚电解质──壳聚糖浓溶液流变学性质研究：浓度、温度、溶剂pH值和外加盐对粘度及流动性的影响

本工作用日本岩本ＲＰＸ－７０５多功能流变仪测定了在不同浓度、温度、溶剂ｐＨ值和外加盐浓度对壳聚糖在甲酸水溶液中其浓溶液粘度η随剪切速率γ的变化关系．讨论了浓度、温度等对溶液粘度、流动活化能Ｅ_γ和流动指数ｎ的影响．发现溶剂ｐＨ值减小或溶液中外加盐浓度增加，溶液粘度变小，ｎ增大，表明非牛顿流动性减弱，并且进一步讨论了零剪切粘度η_０和外加盐浓度Ｃ_ｓ的依赖关系．     

聚电解质──壳聚糖浓溶液流变学性质研究：浓度、温度、溶剂pH值和外加盐对粘度及流动性的影响

本工作用日本岩本ＲＰＸ－７０５多功能流变仪测定了在不同浓度，温度，溶剂ｐＨ值和外加盐浓度对壳聚糖在甲酸水溶液中其浓溶液粘度η随剪切速率γ的变化关系，讨论了浓度，温度等对溶液粘度，流动活化能Ｅγ和流动指数ｎ的影响。发现溶剂ｐＨ值减小或溶液中外加盐浓度增加，溶液粘度变小，ｎ增大，表明非牛顿流动性减弱，并且进一步了零剪切粘度ηｏ和外加盐浓度Ｃｓ的依赖关系。     

分子量对酞侧基聚芳醚酮熔体流变行为的影响

用锥权流变仪及ＤＳＣ的方法研究了５种不同分子量的酞侧基聚芳醚酮（ＰＥＫ—Ｃ）在低剪切速率区（１０－２－１０ｓ－１）的流变行为及其分子量与玻璃化转变温度（Ｔｇ）的关系．结果表明，样品的粘流活化能随分子量的增加而增大，Ｔｇ随分子量的变化是二个线性区，其交点值与所求的样品的临界分子量（Ｍｃ）值相对应．利用测得的零剪切粘度值（η０）首次求得了ＰＥＫ—Ｃ的临界分子量（Ｍｃ）值．同时也讨论了Ｍｃ与温度及η０和Ｔｇ与分子量的关系．     

壳聚糖浓溶液流变性质研究──分子量的依赖性

壳聚糖浓溶液流变性质研究──分子量的依赖性王伟，徐德时（中国科学院长春应用化学研究所高分子物理开放实验室长春１３００２２）关键词壳聚糖，浓溶液，粘度，零剪切粘度，分子量作者曾研究了一些外部条件对壳聚糖浓溶液流变学性质的影响，如浓度、温度、溶剂性质、外...     

聚醚砜流变性能的研究

用锥板流变仪测试了分子量不同的国产聚醚砜（ＰＥＳ）样品的流变性能．结果表明ＰＥＳ具有剪切变稀的特性，所得的粘流活化能与文献报道的ＩＣＩ产品值相近．根据求得的零剪切粘度（η０）与分子量的关系推断样品的分子量已经接近临界分子量（ＭＣ），并利用转换因子αＩ＝η０Ｔ／η０（ＴＲ）绘制了样品的叠合曲线，得到较好的叠加效果，同时还求得了ＷＬＦ方程的两个经验常数Ｃ１和Ｃ２的数值．     

二氧化硅负载胺丙基硅烷电流变流体

研究用二氧化硅负载胺丙基三乙氧基硅烷［ＮＨ２（ＣＨ２）３Ｓｉ（ＯＥｔ）３］作为分散颗粒，制备无水型的电流变（ＥＲ）流体．考察电场强度（Ｅ）、剪切速率（γ·）、分散颗粒含量、分散介质种类以及极性小分子等因素对ＥＲ流体流变性能的影响．结果发现，以硅油为分散介质，含分散颗粒为１５％（ｇ／ｍｌ）的流体，不添加任何活化剂，在γ·为８０６６ｓ－１时，Ｅ从０升至１６６６ｋＶ／ｍｍ，流体的表现粘度（ηａ）从０３９６Ｐａ．ｓ增大到１６６６８Ｐａ．ｓ．γ·提高，ηａ降低．分散颗粒含量增加，ηａ增大．用硅油作分散介质，ＥＲ效应比用矿物油或石蜡油显著．加入极性小分子苯胺，可以增强流体的ＥＲ效应，但随着苯胺含量增多，漏电流密度也增大．     

顺丁橡胶分子结构参数对其浓溶液流变性质的影响

对顺丁橡胶浓溶液作了较为深入的研究,主要讨论了分子量分布和支化因子与顺丁橡胶浓溶液流动行为的关系。用倒沉淀分级的方法进行了大量分级,得到分子量分布较窄的试样;对这些试样用GPC-自动粘度计联用的方法测定了分子量、分子量分布和支化因子,同时用同轴圆筒式粘度计及落球方法测定了这些试样的浓溶液粘度。     

粘度法研究壳聚糖对外加盐的敏感性

聚电解质的特性粘度对外加盐的响应是反映聚电解质对外加盐敏感性的一个重要特征，通过分别测定壳聚糖在不同小分子强电解质（ＮａＣｌ、ＫＣｌ、ＣａＣｌ２、ＢａＣｌ２）和相同小分子强电解质（ＮａＣｌ）但不同离子强度的稀溶液粘度，得到：（１）壳聚糖特性粘度与外加盐的离子强度的平方根的倒数成正比；（２）不同小分子强电解质中阳离子对壳聚糖特性粘度的影响次序是Ｎａ＋＞Ｋ＋＞Ｂａ２＋＞Ｃａ２＋．同时，测算了壳聚糖在不同外加盐浓度中的Ｍａｒｋ Ｈｏｕｗｉｎｋ方程参数α，发现其值皆大于０５，得到了壳聚糖分子链的僵硬性参数Ｂ的值为００７４，揭示了壳聚糖具有较大的分子链刚性和抗盐性能．     

分子结构参数对顺丁胶浓溶液流变性质的影响

本工作用GPC-Automatic Viscometer方法测定了顺丁胶样的分子量、分子量分布和支化因子,用同轴圆筒粘度计及落球法测定了顺丁胶浓溶液的粘度,主要研究了分子量分布和长链支化对顺丁胶浓溶液非牛顿流动的影响。提出了描述不同分子量分布的顺丁胶浓溶液粘度的切变速率依赖性的简单公式,并讨论了长链支化对顺丁胶浓溶液非牛顿流动的影响。     

聚对二炔苯Mark-Houwink方程参数的确定及分子量与分子量分布的研究

通过多个宽分布聚对二炔苯试样的凝胶渗透色谱（ＧＰＣ）和特性粘数（［η］）的测定，应用普适校正原理和Ｗｅｉｓ方法，确定了该聚合物在四氢呋喃溶液中２５℃下的Ｍａｒｋ Ｈｏｕｗｉｎｋ方程参数：Ｋ＝７６２×１０－３，α＝０２６．将这一结果运用到ＧＰＣ谱图的计算，所得［η］与用粘度法实测值比较，所得Ｍｎ与用ＶＰＯ法实测值比较，相对误差６％左右．还研究了聚合反应条件对聚对二炔苯分子量与分子量分布的影响，发现随着聚合时间的延长和聚合温度的升高，聚合物分子链间发生部分交联反应，支化程度加重．聚合过程中还可能存在向单体的链转移反应．     

壳聚糖稀溶液性质的研究

本文在前工作基础上.对不同脱乙酰度壳聚糖在0.2mol/l CH_3COOH+0.1mol/l CH_3COONa的缓冲溶液中进行了分子量、特性粘数、分子尺寸、第二维利系数和扩张因子等稀溶液性质的深入研究.发现Mark-Houwink方程常数K和α有规律地依赖于壳聚糖的脱乙酰度而变化.而且相同分子量时,随着脱乙酰度的增加,壳聚糖在稀溶液中的分子尺寸、特性粘数和扩张因子等增加,而特性比和空间位阻因子随着脱乙酰度的增加而减小.     

乙醇在碳载Pt纳米薄膜电极上吸附和氧化过程研究——II.酸性介质中EQCM和原位FTIR反射光谱

运用电化学循环伏安 ,石英晶体微天平 (EQCM )和原位FTIR反射光谱等方法研究了酸性介质中乙醇在碳载纳米Pt膜电极上吸附和氧化行为 .结果表明 ,乙醇的电氧化与溶液酸碱性及电极表面氧物种有密切的关系 ,并指出乙醇电催化氧化是通过解离吸附产物和反应中间体双途径机理进行的 .在实验条件下 ,经原位FTIR反射光谱检测 ,解离吸附产物为CO ,反应中间体主要有CH3COOH和CH3CHO等物种 .     

New phase separator for extraction-spectrophotometric determination of anionic surfactants with Malachite Green by flow injection analysis

A simple flow injection spectrophotometric method for the determination of anionic surfactants in river water was studied. A three-channel flow system was assembled. The distilled water as a carrier and 5x10(-5) mol l(-1) Malachite Green (MG) dissolved in 0.1 mol l(-1) CH(3)COONa-CH(3)COOH buffer solution (pH 5) were delivered at 1.94 ml min(-1). The mixed solvent (toluene+methylisobutyl ketone (MIBK)=1+1) was pumped at 0.78 ml min(-1). Other conditions were the extraction coil 0.5 mm i.d.x3 m, the reaction temperature 20 degrees C and the sample size 200 mul. The calibration graph was linear in the range 0.1-0.4 ppm at 626 nm. The detection limit (S/N=3) was 18 ppb and a sample frequency of 20 h(-1) was attained. The relative standard deviation (n=7) for 0.4 ppm standard sodium dodecylsulfate (SDS) solutions was 1.1%. And also, new phase separator with a convenient connector was designed. This Fl method was applied to the determination of anionic surfactants in river water.     

Solubility of Ba-Acetate in Mixed Alcoholic Solutions and its Bearing on the Synthesis of Multi-Component Gels

The solubility of Ba-acetate in mixtures of alcohol (ethanol, n-propanol and iso-propanol) and H2O or acetic acid (CH3COOH) have been determined. In the ROH-H2O-Ba(OOCCH3)2 system a small region of miscibility was found. To a saturated solution of 4.8 mol% Ba(OOCCH3)2 in H2O for each additional mol H2O, 0.9 mol iso-propanol or 1.1 mol ethanol can be added without precipitation of Ba(OOCCH3)2. The solubility in alcohol/acetic acid mixtures is higher. For each mol CH3COOH, 2.2 mol iso-propanol, 3.2 mol n-propanol or 4.1 mol ethanol can be added without precipitation of Ba(OOCCH3)2. The results were applied to develop a procedure for the synthesis of gels in the system BaO-Al2O3-SiO2 from metal alkoxides and Ba-acetate. Acetic acid reacts with Al-sec-butoxide to give Al(O-sec-C4H9)3-x(CH3COO)x. Therefore, the solution of Ba-acetate was controlled only over the H2O/alcohol ratio.     

TREATMENT AND RESOURSE REUSE OF INDUSTRIAL WASTEWATER FROM PRODUCTION PROCESS OF PHENYL ACETIC ACID

The effluent from phenyl acetic acid (Ph CH2COOH) production process can be treated with NDA-999 macroporous polymeric adsorbent with about 100% remopval efficiency of Ph CH2COOH,benzyl alcohol(PhCH2OH) and benzaldehyde(PhCOHO)as well as the decrease in Total Organic Carbon(TOC)from 4691mg/l to <300mg/L.3.7kg phCH2COOH and 120kg NaCl will be recovered from per m^3 wastewater and the adsorbent can be reused after being regenerated by NaOH aqueous solution and methanol.Good economic,social and environmental results can be achieved with this method.     

193-nm photodissociation of acryloyl chloride to probe the unimolecular dissociation of CH2CHCO radicals and CH2CCO

The work presented here uses photofragment translational spectroscopy to investigate the primary and secondary dissociation channels of acryloyl chloride (CH2==CHCOCl) excited at 193 nm. Three primary channels were observed. Two C-Cl fission channels occur, one producing fragments with high kinetic recoil energies and the other producing fragments with low translational energies. These channels produced nascent CH2CHCO radicals with internal energies ranging from 23 to 66 kcal/mol for the high-translational-energy channel and from 50 to 68 kcal/mol for the low-translational-energy channel. We found that all nascent CH2CHCO radicals were unstable to CH2CH + CO formation, in agreement with the G3//B3LYP barrier height of 22.4 kcal/mol to within experimental and computational uncertainties. The third primary channel is HCl elimination. All of the nascent CH2CCO coproducts were found to have enough internal energy to dissociate, producing CH2C: + CO, in qualitative agreement with the G3//B3LYP barrier of 39.5 kcal/mol. We derive from the experimental results an upper limit of 23 +/- 3 kcal/mol for the zero-point-corrected barrier to the unimolecular dissociation of the CH2CHCO radical to form CH2CH + CO.     

高效液相色谱法分析生漆多糖中的单糖组成

采用μ－ＢｏｎｄａｐａｋＮＨ２ＴＭ色谱柱,以乙腈∶水∶甲醇（７０∶２５∶５,Ｖ／Ｖ）为流动相,利用示差折光检测器的高效液相色谱法对湖北毛坝大木、毛坝小木和建始３种生漆中漆多糖的单糖组成成分进行了直接分离分析,方法简便、快速、重现性好,回收率在９８．８％～１０３．６％之间,相对标准偏差在５％以下。     

A general strategy for the experimental study of the thermochemistry of protic ionic liquids: enthalpy of formation and vaporisation of 1-methylimidazolium ethanoate

A general strategy to determine enthalpies of formation of protic ionic liquids, based solely on enthalpy of solution measurements, was conceived and tested for 1-methylimidazolium ethanoate, leading to Δ(f)H°(m){[Hmim][O(2)CCH(3)], 1} = -(425.7 ± 1.2) kJ mol(-1). This result in conjunction with the enthalpy of formation of gaseous 1-methylimidazole (mim) proposed in this work, Δ(f)H°(m)(mim, g) = 126.5 ± 1.1 kJ mol(-1), and Δ(f)H°(m)(CH(3)COOH, g) taken from the literature, allowed the calculation of the enthalpy of the vaporisation process [Hmim][O(2)CCH(3)](l) → mim(g) + CH(3)COOH(g) as Δ(vap)H°(m){[Hmim][O(2)CCH(3)]} = 119.4 ± 3.0 kJ mol(-1). The agreement between this value and Δ(vap)H°(m){[Hmim][O(2)CCH(3)]} = 117.3 ± 0.5 kJ mol(-1), obtained for the direct vaporisation of [Hmim][O(2)CCH(3)], by Calvet-drop microcalorimetry, gives a good indication that, as previously suggested by Fourier transform ion cyclotron resonance mass spectrometry, Raman spectroscopy, and GC-MS experiments, the vaporisation of [Hmim][O(2)CCH(3)] essentially involves a proton transfer mechanism with formation of the two volatile neutral precursor molecules (mim and CH(3)COOH). Although being a low ionicity protic ionic liquid, [Hmim][O(2)CCH(3)] was chosen to validate the methodology proposed here, since its vaporisation mechanism has been unequivocally demonstrated by different methods and for different pressure ranges.     

The cysteine radical cation: structures and fragmentation pathways

A theoretical study on the structures, relative energies, isomerization reactions and fragmentation pathways of the cysteine radical cation, [NH(2)CH(CH(2)SH)COOH].+, is reported. Hybrid density functional theory (B3LYP) has been used in conjunction with the 6-311++G(d,p) basis set. The isomer at the global minimum, Captodative-1, has the structure NH(2)C.(CH(2)SH)C(OH)(2)+; the stability of this ion is attributed to the captodative effect in which the NH(2) functions as a powerful pi-electron donor and C(OH)(2)+ as a powerful pi-electron acceptor. Ion Distonic-S-1, H(3)N(+)CH(CH(2)S.)COOH, in which the radical is formally situated on the S atom, is higher in enthalpy (DeltaH degrees (0)) than Captodative-1 by 6.1 kcal mol(-1), but is lower in enthalpy than another isomer Distonic-C-1, H(3)N(+)C.(CH(2)SH)COOH, by 8.2 kcal mol(-1). Isomerization of the canonical radical cation of cysteine, [H(2)NCH(CH(2)SH)COOH].+, (Canonical-1), to Captodative-1 has an enthalpy of activation of 25.8 kcal mol(-1), while the barrier against isomerization of Canonical-1 to Distonic-S-1 is only 9.6 kcal mol(-1). Two additional transient tautomers, one with the radical located at C(alpha) and the charge on SH(2), and the other a carboxy radical with the charge on NH(3), are reported. Plausible fragmentation pathways (losses of small molecules, CO(2), CH(2)S, H(2)S and NH(3), and neutral radicals COOH. , HSCH(2). and NH(2).) from Canonical-1 are examined.     

Fabrication of Hard Dextran DEAE: Adsorption Equilibria of BSA

A hard dextran-DEAE ion exchanger (Hard Dextran DEAE) was developed. It is hard and keeps good properties of dextran-DEAE for protein separation. It is not compressed in a column and can be used in much wider range of flow rate in the column than the commercial hard gel, DEAE Sepharose Fast Flow made of agarose. The saturation capacity of BSA on Hard Dextran DEAE is about 1.7 times of that on DEAE Sepharose Fast Flow at pH 6.9. Equilibrium isotherm for adsorption of BSA depends on pH considerably. When pH 5.5, the equilibrium isotherm is correlated by the Langmuir equation. When pH 5.05, the isotherm is correlated by the Freundlich equation. The higher the concentration of NaCl is, the smaller the amount of BSA adsorbed. When the concentration of NaCl is higher than 100 mol m–3 at pH 6.9 and 50 mol m–3 at pH 4.8, BSA was not adsorbed on the resin. This may suggest that BSA is adsorbed by electrostatic attraction. About 100 mol m–3 NaCl aqueous solution can be used as an eluant of proteins.